Fungicidal carboxamides

ABSTRACT

Compounds of Formula I are disclosed which are useful as fungicides  
                 
wherein 
 
Q is  
                 
         X is —O—, —CH(R 11 )— or ═C(R 11 )—;    R 1  is H or C 1 -C 2  alkyl;    R 2  is H; C 1 -C 6  alkyl; C 3 -C 6  cycloalkyl; or phenyl optionally substituted with halogen, cyano, C 1 -C 2  alkyl or C 1 -C 2  alkoxy;    and R 3 -R 11  are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula I and a method for controlling plant diseases caused by fungal plant pathogens which involves applying an effective amount of a compound of Formula I.

BACKGROUND OF THE INVENTION

This invention relates to certain N-(arylpropyl), N-(aryloxyethyl), and N-(arylalkyl)-carboxamides, their agriculturally suitable salts and compositions, and methods of their use as fungicides.

The control of plant diseases caused by fungal plant pathogens is extremely important in achieving high crop efficiency. Plant disease damage to ornamental, vegetable, field, cereal, and fruit crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.

U.S. Pat. No. 4,710,518 discloses compounds of Formula i and compositions thereof as fungicides:

wherein

X is halogen;

n is 1 or 2;

R¹ is hydrogen, halogen or lower alkyl;

R² is lower alkyl, halogen-substituted lower alkyl or hydrogen; and

R³ is hydrogen or lower alkyl.

U.S. Pat. No. 4,946,847 discloses compounds of Formula ii, and compositions and method of use thereof, as fungicides:

wherein

R is C₂-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl or C₃-C₆ cycloalkyl; and

X is Cl, Br, CF₃ or lower fluoroalkoxy group.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula I (including all geometric and stereoisomers), agricultural compositions containing them and their use as fungicides:

wherein

Q is

X is —O—, —CH(R¹¹)— or ═C(R¹¹)—;

R¹ is H or C₁-C₂ alkyl;

R² is H; C₁-C₆ alkyl; C₃-C₆ cycloalkyl; or phenyl optionally substituted with halogen, cyano, C₁-C₂ alkyl or C₁-C₂ alkoxy;

R³ is H, C₁-C₃ alkyl optionally substituted with halogen or CN;

R⁴ is H or C₁-C₂ alkyl; or

R³ and R⁴ can be taken together as —CH₂CH₂CH₂— or —CH₂CH₂CH₂CH₂—;

R⁵ is H, C₁-C₂ alkyl optionally substituted with halogen or CN;

R⁶ is C₂-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₂-C₈ alkynylalkenyl or C₃-C₈ cycloalkyl, each optionally substituted with halogen;

R⁷ is H, CN, halogen, C₁-C₂ haloalkoxy or C₁-C₂ haloalkylthio; or C₁-C₄ alkyl, C₂-C₄ alkenyl or C₂-C₄ alkynyl, each optionally substituted with halogen or CN;

R⁸, R⁹ and R¹⁰ are each independently H, halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl, or Si(CH₃)₃; and

R¹¹ is H, C₁-C₅ alkyl, C₂-C₅ alkenyl or C₂-C₅ alkynyl.

DETAILS OF THE INVENTION

In the above recitations, the term “alkyl”, used in compound words such as “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl or i-propyl. The term “alkyl”, used alone includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl, hexyl, heptyl or octyl isomers. “Alkenyl” includes straight-chain or branched alkenes such as vinyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl, hexenyl, heptenyl and octenyl isomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl, hexynyl, heptynyl and octynyl isomers. “Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. “Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. “Alkynylalkenyl” is a compound word and includes straight-chain or branched alkyne substituted on a straight-chain or branched alkene. Examples of “alkynylalkenyl” include H₂C═CHC(CH₃)(C≡CH) and HC≡CCH═CHC(CH₃)₂—.

In the above recitations, the term “alkoxy”, used in compound words such as “haloalkoxy” or “haloalkylthio” includes methyl and ethyl. Examples of “haloalkoxy” include CF₃CH₂O, CF₃O, CHF₂CF₂O, HF₂CO and CCl₃CCl₂O. Examples of “haloalkylthio” include CF₃S, HF₂CS, CCl₃S, CHF₂CF₂S and CF₃CH₂S.

The term “halogen”, either alone, when a group is “optionally substituted with halogen” or in compound words such as “haloalkyl”, “haloalkoxy” or “haloalkylthio”; includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl” or when a group is “optionally substituted with halogen”, said alkyl or group may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F₃C, ClCH₂, CF₃CH₂ and CF₃CCl₂. Examples of an alkyl group “optionally substituted with halogen” include CH(F)═CHC(CH₃)(CH₂F) and CH₂═CHC(CH₃)(CH₂F).

The total number of carbon atoms in a substituent group is indicated by the “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 6. For example, C₁-C₃ alkyl designates methyl through propyl. When a group contains a substituent which can be hydrogen, for example R¹ or R³, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.

Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.

Of note are compounds where R⁷ is other than H, especially when Z is Z-1. Also of note are compounds where R⁷ is hydrogen and R⁸ is other than hydrogen and when Z is Z-1 is attached to the carbon adjacent to the R⁷ substituted carbon. Further of note are compounds where the carbon attached to R¹ has the (R) configuration.

Also of note are compounds wherein R¹ is H or CH₃; R² is H or CH₃; R⁶ is C₂-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl or C₃-C₆ cycloalkyl each optionally substituted with halogen; and R⁷ is H, CN, halogen, C₁-C₄ haloalkyl, C₁-C₄ alkyl, C₂-C₄ alkenyl or C₂-C₄ alkynyl each optionally substituted with halogen or CN.

Compounds of the invention include compounds of Formula Ia, Ib and Ic.

Preferred compounds for reasons of better activity and/or ease of synthesis are:

Preferred 1. Compounds of Formula I above and agriculturally suitable salts thereof,

-   -   wherein:     -   Q is Q-1;     -   R¹ is CH₃;     -   R² is H;     -   R³ is CH₂CH₃; and     -   R⁴ is CH₃.

Preferred 2. Compounds of Preferred 1 wherein:

-   -   Z is Z-1 or Z-4;     -   R⁷ is H, halogen, CN, C₁-C₄ alkyl or C₂-C₄ alkenyl;     -   R⁸ is H or F and is in the para position with respect to X when         Z is Z-1; and     -   R⁹ is in the para position with respect to R⁷ when Z is Z-1.

Preferred 3. Compounds of Preferred 1 wherein:

-   -   Z is Z-2 or Z-3; and     -   R⁷ is H, halogen, CN, C₁-C₃ alkyl or C₂-C₄ alkenyl.

Preferred 4. Compounds of Formula I above and agriculturally suitable salts thereof,

-   -   wherein:     -   Q is Q-2;     -   R¹ is CH₃;     -   R² is H or phenyl optionally substituted with halogen, cyano,         C₁-C₂ alkyl or C₁-C₂ alkoxy; and     -   R⁶ is C₂-C₆ alkyl or C₂-C₆ alkenyl each optionally substituted         with halogen.

Preferred 5. Compounds of Preferred 4 wherein:

-   -   Z is Z-1 or Z-4;     -   R⁷ is H, halogen, C₁-C₃ alkyl, C₂-C₄ alkenyl or C₂-C₄ alkynyl;     -   R⁸ is H or F and is in the para position with respect to X when         Z is Z-1; and     -   R⁹ is in the para position with respect to R⁷ when Z is Z-1.

Preferred 6. Compounds of Preferred 4 wherein:

-   -   Z is Z-2 or Z-3; and     -   R⁷ is H, halogen, C₁-C₄ alkyl, C₂-C₄ alkenyl or C₂-C₄ alkynyl.

This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds.

This invention also relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of the compounds of the invention (e.g., as a composition described herein). The preferred methods of use are those involving the above preferred compounds.

DETAILS OF THE SYNTHESIS

The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1. The definitions of Q, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, X and Z in the compounds of Formulae I-XXXIII below are as defined above in the Summary of the Invention.

When A is OH, the amine of formula II is condensed with the carboxylic acid of Formula III in the presence of a dehydrating reagent, such as N,N′-dicyclohexylcarbodiimide (DCC) or carbonyl diimidazole (CDI), in the presence of an inert solvent. The process can be carried out over a wide temperature range in a wide variety of solvents. Generally, the condensation is carried out at a temperature between 20° C. and the boiling point of the reaction mixture, preferably about 100° C., for 0.1 to 72 h. Examples of suitable solvents include methylene chloride, toluene, diethyl ether, tetrahydrofuran, acetone and acetonitrile.

When A is chlorine, the amine of Formula II is condensed with the carboxylic acid chloride of Formula III in the presence of an acid acceptor such as triethylamine, in an inert solvent. Suitable reaction temperatures, times, solvents, and pressures are the same as described for the condensation wherein A is OH.

The amines of Formula II are known or can be prepared by a variety of methods. Formula II amines can be prepared from carbamates IV wherein R¹² is typically t-butyl or benzyl or from V in which Y is typically phenyl (forming a phthalimide ring) or bis-t-butoxycarbonyl (forming a bis-t-butoxycarbonyl protecting group). The removal of the carbamate and phthalimide protecting groups of IV and V to form II can be effected by methods set out in the literature such as those referenced in Greene, T. W. Protective Groups in Organic Synthesis; John Wiley & Sons, New York, N.Y., (1991), Chapter 7.

The compounds of Formulas IVa and Va in which X is carbon with a double bond attachment are subsets of Formula IV and V compounds and can be prepared by treatment of protected amines of Formulas VIa and VIb, respectively, with aromatic bromides or iodides (for the cases in which Z is phenyl or thiophene) of Formula VII and 1-10 mole % of an appropriate Pd (II) catalyst. Appropriate catalysts include PdCl₂ and Pd(OAc)₂ complexed with a 2-4 fold excess of a phosphine ligand such as triphenylphosphine. The reactions are performed between 0° C. and 100° C. with a 1-3 molar equivalents of a base such as K₂CO₃ or triethylamine. Oftentimes 10-50 mole % of an ammonium phase transfer catalyst is used in the reaction mixture. Typical solvents include acetonitrile or dimethylformamide.

Formula VI compounds are made from the corresponding unprotected amines by methods set out in the literature such as those referenced in Greene, T. W., Protective Groups in Organic Synthesis; John Wiley & Sons, New York, N.Y., (1991), Chapter 7. Alternatively, they may be prepared by displacement of a leaving group LG from compounds of Formula VIII with carbamates or diimides of Formula IXa or IXb in the presence of a base such as alkoxide salts as potassium t-butoxide, hydride salts as sodium hydride, or amine bases as diisopropyl ethylamine. Typical leaving groups LG includes chloride, bromide, iodide, (methylsulfonyl)oxy or [(4-methylphenyl)sulfonyl]oxy.

Formula VII, VIII and IX compounds are commercially available or are synthesized by procedures set out in the literature.

Alternatively, compounds of Formula IVa (for the cases in which Z is phenyl or thiophene) can be made from compounds of Formula XXXV by treatment with a phosphine such as triphenylphosphine in the presence of aromatic aldehydes and ketones of Formula XXXVI. The reactions are run in ethereal solvents such as glyme or tetrahydrofuran, hydrocarbon solvents such as toluene or protic solvents such as isopropyl alcohol or ethanol at temperatures ranging between 20° C. and 150° C. Formula XXXV and XXXVI are either commercially available or easily synthesized by methods set out in the literature.

Compounds of Formulas IVb and Vb are a subset of Formula IV and Formula V compounds in which X is carbon with a single bond attachment and can be prepared from compounds of Formulas IVa and Va, respectively, by hydrogenation over an appropriate transition metal catalyst such as palladium, platinum or rhodium. Typically the catalyst is deposited over an inert support such as carbon, alumina or calcium carbonate. The hydrogenations are carried out in protic solvents such as ethanol or non-protic solvents such as tetrahydrofuran or ethyl acetate. Pressures of 1-10 torr of hydrogen are required. The hydrogenations are run at 25° C. but may be run at temperatures up to 100° C.

Alternatively, compounds of Formula IIb in which Z is phenyl or thiophene and X is carbon with a single bond attachment can be prepared from compounds of Formula X by reductive amination with an excess of an ammonium halide or acetate salt in the presence of a 1-10 equivalents of hydride reducing reagent such as sodium or tetrabutyl cyanoborohydride or sodium triacetoxyborohydride. The reaction can be run in protic solvents such as methanol or in aprotic solvents such as tetrahydrofuran or dichloromethane. An acid catalyst such as HCl or p-toluenesulfonic acid is often added portionwise so as to maintain a pH of 3-5 as determined by a pH meter or an indicator dye such as bromocresol green or methyl orange. Typical temperatures for the reductive aminations range from −5° C. to 60° C.

Compounds of Formula X can be prepared from compounds of Formula XI in which Z is phenyl or thiophene, by hydrogenation under the conditions described for the conversion of compounds IVa and Va to compounds IVb and Vb. Compounds of Formula XI can be prepared by olefination of compounds of Formula XII in which Z is phenyl or thiophene with an appropriate triphenylphosphonium ylide or an appropriate phophonate anion. The olefination reactions are typically carried out in ethereal solvents such as tetrahydrofuran or dimethoxyethane or in polar aprotic solvents such as dimethylsulfoxide or dimethylformamide at temperatures ranging from 0 to the 100° C. The ylides and phosphonate anions are generated with alkoxide or hydride bases respectively and by methods set out otherwise in the literature (see March J. Advanced Organic Chemistry; John Wiley & Sons: New York, (1992); 4th Ed., pp 956-963).

Compounds of Formula IVb or Vb in which Z is pyrrolyl can be prepared by displacement of the leaving group LG of compounds of Formulas XIIIa or XIIIb in the presence of an acid acceptor which can be a tertiary amine such as triethylamine, an alkoxide such as potassium t-butoxide or a carbonate such as potassium carbonate. The leaving group LG is as described for Formula VIII compounds. The displacements can be carried out in polar aprotic solvents such as dimethylformamide or dimethylsulfoxide, ethereal solvents such as tetrahydrofuran or dioxane, or in protic solvents such as ethanol. Reaction temperatures can vary from 20° C. to 150° C.

Compounds of Formula XIII can be prepared from the compounds of Formulas XIVa or XIVb by standard methods for the conversion of alcohols to halides (March, J. Advanced Organic Chemistry; John Wiley & Sons: New York, (1992); 4th Ed., pp 431-433) and for the conversion of alcohols to sulfonates (March, J. Advanced Organic Chemistry; John Wiley & Sons: New York, (1992); 4th Ed., pp 498-499). Compounds XIV can, in turn, be prepared from the aminoalcohol by methods set out in the literature such as those referenced in Greene, T. W. Protective Groups in Organic Synthesis; John Wiley & Sons, New York, N.Y., (1991), Chapter 7.

Compounds of Formula IVc and Vc are a subset of compounds of Formula IV in which X is O and can be prepared from compounds of Formula XVa and XVb, respectively, by displacement of the leaving group LG with compounds of Formula XVI under conditions as described for the conversion of XIII to IVb and Vb. The leaving group LG is as described for Formula VIII compounds. Formula XVa and XVb compounds can be prepared from the corresponding alcohols XVIIa and XVIIb as described for Formula XIII compounds. Alternatively, IVc and Vc can be prepared directly from XVIIa and XVIIb, respectively, and XVI in the presence of 1-2 equivalents of triphenylphosphine and 1-2 equivalents of diethylazodicarboxylate. The reaction is generally run in an inert solvent such as methylene chloride or tetrahydrofuran at a temperature range of 0° C. to 100° C. Compounds of Formula XVI are generally commercially available or can be prepared by methods set out in the literature. For a review of literature methods for when Z is pyrrolyl, see Achesson, R. M. Adv. Heterocycl. Chem. (1990), 51, 115-119. Compounds of Formula XVII are prepared from the corresponding aminoalcohol as described for the preparation of compounds of Formula XIV.

Alternatively, compounds of Formula IVc in which Z is phenyl or thiophene can be prepared by reaction of compounds XVIIa with base and an activated aryl fluoride of Formula XVIII. Appropriate bases include hydride salts such as sodium hydride, amine salts such as lithium diisopropylamine and alkoxide salts such as potassium t-butoxide. Solvents for the reaction can include ethereal solvents such as tetrahydrofuran or polar aprotic solvents such as dimethylformamide. Reaction temperatures can vary from −20° C. to 150° C. The reaction is facilitated for the cases in XVIII wherein at least one of R⁷, R⁸, R⁹, or R¹⁰ is an electron withdrawing group such as CN or halogen.

Compounds of Formula IIIa, a subset of Formula III compounds wherein A is OH, can be prepared from the corresponding esters of Formula XIX wherein R¹³ is C₁-C₅ alkyl or optionally substituted benzyl via standard methods for ester hydrolysis (see Greene, T. W. Protective Groups in Organic Synthesis; John Wiley & Sons, New York, N.Y., (1991), pp 227-260).

Compounds of Formula XIXa, a subset of Formula XIX compounds, can be prepared from compounds of Formula XX by treatment with excess dichlorocarbene. Dichlorocarbene can be generated in chloroform solvent and reacted with XX in a biphasic mixture with 5-20 equivalents of sodium or potassium hydroxide facilitated by 1-20 mole % of a tetraalkyl ammonium halide or a crown ether phase transfer catalyst. The reaction is run at temperatures ranging from 0° C. to 60° C. The conversion of XX to XIXa can also be effected by treatment with 1-5 equivalents of the alkali metal salts of trichloroacetic acid in ethereal solvents such as diglyme or dioxane or aromatic hydrocarbon solvents such as benzene or toluene or under neat conditions. The reaction temperatures can vary from 60° C. to 150° C. Addition of 1-20 mole % of a phase transfer catalyst such as 18-crown-6 or tetrabutyl ammonium chloride can enhance the reaction. Alternatively, the conversion of XX to XIX can be effected by treatment with 1-5 equivalents of methyl or ethyl esters of trichloroacetic acid in the presence of 1-5 equivalents of sodium methoxide or sodium ethoxide. Appropriate solvents include hydrocarbons such as pentane or cyclohexane, ethers such as tetrahydrofuran or dimethoxyethane or aromatic hydrocarbons such as benzene or toluene. The temperature of the reaction can vary from −20° C. to 120° C.

Compounds of Formula XX are prepared via condensation of compounds of Formula XXI and XXII. The conditions for such condensations are described in the references contained in March, J. Advanced Organic Chemistry; John Wiley & Sons: New York, (1992); 4th Ed., pp 944-945.

Alternatively, compounds of Formula IIIb, a subset of Formula IIIa compounds, can be prepared by oxidation of compounds of Formula XXIII via a variety of methods set out in the literature for the oxidation of alcohols to acids (see Larock, R. C. Comprehensive Organic Transformations; VCH Publishers: New York, (1989), pp 834-837). The dichlorocyclopropane of XXIII can be introduced by reaction of compounds of Formula XXIV via conditions described for the conversion of XX to XIXa.

The conversion of XXIV to XXIII can sometimes be more efficiently mediated by the use of protecting group chemistry. Thus the alcohol of XXIV can be converted to an ether XXV in which PG can be an alkyl, benzyl or silyl protecting group. Conversion to XXIII is effected by subsequent cyclopropanation to XXVI via conditions described for the conversion of XIX to IIIa followed by removal of the protecting group. Appropriate protecting groups PG and the condition for their introduction and removal are described in Greene, T. W. Protective Groups in Organic Synthesis; John Wiley & Sons, New York, N.Y., (1991), pp 10-86.

Compounds of Formula XXIV can be prepared from compounds of Formula XXVII by addition of 2-5 equivalents of Grignard reagents XXVIII and quenching via the dropwise addition of an excess of either a protic solvent such as water, methanol or acetic acid optionally containing a dissolved proton donor such as ammonium chloride or hydrogen chloride or a reagent of Formula XXIX in which LG is a leaving group as described for Formula VIII compounds. The reaction is performed in ethereal solvents such as diethyl ether or tetrahydrofuran at temperatures ranging from 0° C. to 60° C. with quenching carried out at temperatures ranging from −20° C. to 30° C.

Alternatively, compounds of Formula XXIV can be prepared from compounds of Formula XXX by treatment with a 2-5 equivalents of a Grignard or zinc organometallic reagent of Formula XXXI (M is a magnesium halide or a zinc halide) in the presence of 1-10% of a transition metal catalyst such as ((C₆H₅)₃P)₂NiCl₂ or ((C₆H₅)₃P)₄Pd. The reaction is typically run in an ethereal solvent such as ethyl ether or tetrahydrofuran or a polar aprotic solvent such as dimethylformaride at temperatures ranging from −20° C. to 60° C.

Compounds of Formula XXX can be prepared as described for the preparation of compounds of Formula XXIV with the modification that the reaction mixture is quenched with an excess of either I₂ or Br₂ added dropwise in the chosen reaction solvent.

Compounds of Formula XIXb, as subset of Formula XIX compounds, are well known in the literature (see, for example, Alexander, E. R.; McCollum, J. D. and Pour, D. E. J. Org. Chem. (1950), 72, 4791-4972; Stevens, R. V.; Christenson, C. G., Edmonson, W. L.; Kaplan, M.; Reid, E. B.; Wentlant, M. P. J. Am. Chem. Soc. (1971), 93, 6624-6637; and Anonymous, USA Res. Discl. (1985), 55, 249) and can be prepared by addition of a 1-2 equivalents of an alkyl magnesium, copper, zinc or lithium reagent of Formula XXXII in which R¹⁶ is C₁-C₄ alkyl, C₂-C₄ alkenyl or C₂-C₄ alkynyl optionally substituted with CN to compounds of Formula XXXIII. R¹⁴ and R¹⁵ in XXXIII are independently H, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl or C₃-C₆ cycloalkyl each optionally substituted with halogen. The reaction is typically run in an ethereal solvent such as diethyl ether or tetrahydrofuran at temperatures ranging from −20° C. to 60° C. Optionally, a Cu (I) catalyst (I -10 mole %) such as copper (I) halide can be added to facilitate the reaction. Alternatively, XXXIII can be hydrogenated to XIXb under the conditions described for the conversion of IVa and Va to IVb and Vb. Compounds of Formula XXXIII are well known in the literature and are prepared by Knoevenagle condensation of cyanoacetic esters with aldehydes and ketones (see Jones, G. Organic Reactions John Wiley & Sons: New York, (1967); Vol. 15 pp 238-244).

Compounds of Formula IIIc, a subset of Formula IIIa compounds in which Q is Q-2; R¹⁴ and R¹⁵ are as described previously; and R¹⁷, R¹⁸, R¹⁹ are independently halogen, C₁-C₂ alkyl, C₂ alkenyl, C₂ alkynyl each optionally substituted with halogen can be prepared from compounds of Formula XXXIV. The rearrangement of Formula XXXIV compounds to Formula IIIc compounds can be carried out by procedures set out in the literature (see March, J. Advanced Organic Chemistry; John Wiley-& Sons: New York, (1992); 4th Ed., pp 1136-1141). Typically XXXXIV is treated with 1 equivalent of a lithium or potassium amide or alkoxide base such as lithium diisopropyl amine or potassium t-butoxide in an inert solvent such as tetrahydrofuran or toluene at temperatures ranging from −78° C. to 150° C. Additionally, the intermediacy of silyl ketene acetals can be involved for the conversion by heating XXXIV to reflux in a solvent such as hexamethyldisilazane or in an inert solvent such as benzene or toluene in the presence of 1-10 equivalents of hexamethyldisilazane. The product of the silyl ketene acetal mediated rearrangement is a silyl ester which can be converted to the acid by acid or base hydrolysis.

Compounds of Formula XXXIV can be prepared from compounds of Formula XXXV by standard conditions of esterification (see March, J. Advanced Organic Chemistry; John Wiley & Sons: New York, (1992); 4th Ed., pp 392-401). Formula XXXV compounds are generally commercially available or readily synthesized by methods set out in the literature.

It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I.

One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. ¹H NMR spectra are reported in ppm downfield from tetramethylsilane; s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet, dd=doublet of doublets, dt=doublet of triplets, br s=broad singlet.

EXAMPLE 1

Step A: Preparation of (cis)-2-ethyl-2-buten-1-ol

A solution of 800 mL of 3.0 M ethylmagesium bromide in ether was added dropwise to a solution of 40 ml (690 mmol) propargyl alcohol and 13.1 g (69 mmol) of copper iodide in 1 L ether cooled to 0° C. The mixture was allowed to warm to room temperature and stirred for 3 days. After cooling to 0° C., 295 g of iodine was added portionwise. The mixture was acidified with concentrated HCl and partitioned between ether and water. The ether was separated and washed with saturated aqueous NaHSO₃, water and brine. Drying (MgSO₄) and removal of solvent gave an oil which was distilled at 5 torr. The fraction boiling from 74-81° C. was the product, (trans)-2-(iodomethylene)-1-butanol, 49 g. This fraction was dissolved in 500 mL ether along with 7.8 g (12 mmol) of bis-triphenylphospine nickel(II) chloride and cooled to 0° C. A solution of 231 mL of 3.0 M methylmagnesium bromide in ether was added dropwise. The mixture was allowed to warm to room temperature and stirred overnight. Quenching first with 1N HCl and then with concentrated HCl was followed by partitioning between ether and water. The ether was separated and washed with water, aqueous NaHSO₃, water and brine. Drying (MgSO₄) and removal of solvent gave an oil which was distilled at 0.5 torr. The fraction boiling from 83-96° C. was the product, (cis)-2-ethyl-2-buten-1-ol, 9.6 g.

Step B: Preparation of (cis)-2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid

A solution of 9.6 g (96 mmol) of (cis)-2-ethyl-2-buten-1-ol,-and 0.44 g benzyltriethyl ammonium chloride in 200 mL of chloroform was cooled to 0° C. and a solution of 95.5 mL of 50% sodium hydroxide was added dropwise. After stirring 2 h, the mixture was diluted with water and extracted 3 times with ether. The ether was dried (MgSO₄) and stripped to give 19.4 g of an oil that was used further without purification. A solution of 16.7 g (91.7 mmol) of the oil was dissolved in 100 mL acetone and cooled to 0° C. A solution of 18.3 g (183 mmol) of CrO₃ in 125 mL of 25% H₂SO₄ was added dropwise. After stirring 5 min, a solution of saturated aqueous NaHSO₃ was added dropwise. The mixture was extracted with ether. The ether was washed with water and 3 times with 1N sodium hydroxide. The base extracts were acidified and extracted 3 times with ether. The ether was dried (MgSO₄) and stripped to give 9.32 g of product (cis)-2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid as an oil that slowly solidified, mp 68-70° C., ¹H NMR (CDCl₃): δ 1.0 (t, 3H), 1.25 (d, 3H), 1.25 (m, 1H), 2.25 (m, 1H), 2.35 (q, 1H).

Step C: Preparation of (cis)-2,2-dichloro-1-ethyl-3-methyl-N-(3-phenylpropvy)cyclopropanecarboxamide

A solution of 2.06 g (10.5 mmol) of(cis)-2,2-dichloro-1-ethyl-3-methyl 1-cyclopropane carboxylic acid in 10 mL thionyl chloride was heated at reflux for 30 min. Solvent was removed in vacuo. The residue was dissolved in 18 mL of dichloromethane. A portion (5 mL, 2.55 mmol) of this solution was added to a solution of 0.4 mL (2.8 mmol) 3-phenyl-1-propylamine and 0.33 mL (3.05 mmol) triethylamine in 25 mL dichloromethane. After stirring at room temperature overnight, the mixture was diluted with ethyl acetate and washed with water and brine. Drying (MgSO₄) and removal of solvent gave an oil which was chromatographed on silica gel (2:1 hexanes/ether) to give 260 mg of the title compound, mp 66-70° C., ¹H NMR (CDCl₃) 1.05 (t, 3H), 1.3(d, 3H), 1.5 (m, 1H), 1.8-2.0 (m, 4H), 2.65 (t, 2H), 3.3-3.5 (m, 2H), 5.6 (br s, 1H), 7.2-7.4 (m, 5H).

EXAMPLE 2

Step A: Preparation of (trans)-2-ethyl-2-buten-1-ol

A solution 1070 mL (2.15 mol) of 2.0 M ethylmagnesium chloride in ether was added dropwise to a solution of 50 mL (720 mmol) of 2-butyn-1-ol and 14.9 g (78 mmol) of copper iodide in 1L of 4:1 ether/tetrahydrofuran at 0° C. under an argon atmosphere. The solution was heated at reflux for 6 days. A solution of 65 mL of 25% by weight ethylmagnesium chloride in tetrahydrofuran was added. Heating at reflux was continued for another day. The reaction was quenched by dropwise addition of saturated aqueous NH₄Cl and the mixture was partitioned between water and ether. The ether layer was separated and washed with water. Drying (MgSO₄) and removal of solvent gave 53.5 g of (trans)-2-ethyl-2-buten-1-ol as a mobile oil.

Step B: Preparation of (trans)-2,2-dichloro-1-ethyl-3-methylcyclopropanemethanol

Imidazole (13.6 g, 200 mmol) was added portionwise to a solution of 8.0 g (80 mmol) of (trans)-2-ethyl-2-buten-1-ol and 14.5 g (96 mmol) of t-butyldimethylsilyl chloride in 20 mL of DMF and the mixture was stirred at room temperature overnight. The solution was poured into water and extracted with ethyl acetate. The ethyl acetate was washed 4 times with water and with brine. Drying (MgSO₄) and removal of solvent gave 17 g of (trans)-(1,1-dimethylethyl)[(2-ethyl-2-butenyl)oxyldimethylsilane as a mobile oil. A solution of 10 g (46.6 mmol) of the oil and 0.21 g of benzyl triethylammonium chloride in 100 mL CHCl₃ was cooled to −5° C. A solution of 45 mL (85 mmol) of 50% sodium hydroxide was added dropwise and the mixture was warmed to room temperature and stirred for 3 h. The mixture was diluted with methylene chloride and washed with 3 times with water, 1N HCl and brine. Drying (MgSO₄) and removal of solvent gave 14 g of (trans)-[(2,2-dichloro-1-ethyl-3-methylcyclopropyl)methoxy](1,1-dimnethylethyl)dimethylsilane as a viscous oil. This oil was dissolved in 200 mL of ethanolic 1% HCl which was heated at reflux for 2.5 h. Solvent was removed and the residue was diluted with methylene chloride and washed with water and brine. Drying (MgSO₄) and removal of solvent gave 8.95 g of (trans)-2,2-dichloro-1-ethyl-3-methylcyclopropanemethanol.

Step C: Preparation of (trans)-2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid

Sodium periodate (21 g, 98 mmol) was added portionwise to a solution of 8.91 g (4.92 mmol) of (trans)-2,2-dichloro-1-ethyl-3-methyl-cyclopropanemethanol and 0.22 g (1 mmol) of RuCl₃.H₂O in 100 mL of 1:1 acetonitrile/carbon tetrachloride and 70 mL of water. After stirring 3 h, the mixture was diluted with methylene chloride and washed with water and brine, dried (MgSO₄) and stripped. The residue was dissolved in ether and washed 2 times with 1N sodium hydroxide and with water. The combined aqueous layers were acidified and extracted 2 times with ether. The ether was washed with water and dried (MgSO₄). Removal of solvent gave 6.1 g of (trans)-2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid as an oil that slowly solidified, mp 61-63° C.

Step D: Preparation of (R)-2-[1-methyl-2-[(methylsulfonyl)oxy]ethyl]-1H-isoindole-1,3(2H)-dione

Methanesulfonyl chloride (9.4 mL, 68 mmol) was added to a solution of 12.6 g (61.5 mmol) of(R)-2-(2-hydroxy-1-methylethyl)-1H-isoindole-1,3(2H)-dione (Becker, Y. J. Org. Chem. (1980), 45 (11), pp 2145-2151) and 5.23 mL (67.6 mmol) of methanesulfonyl chloride, and the mixture was stirred at room temperature overnight. Solvent was removed, and the residue was dissolved in ethyl acetate which was washed with water and brine. Drying (MgSO₄) and removal of solvent gave 17 g of a tan oil which slowly solidified. Recrystallization from n-butylchloride gave (R)-2-[1-methyl-2-[(methylsulfonyl)oxy]ethyl]-1H-isoindole-1,3(2H)-dione as a white solid, mp 75-77° C.

Step E: Preparation of 5-chloro-6-methyl-2-pyridinamine 1-oxide, hydrochloride

To a solution of 110 g (666 mmol) of 5-chloro-6-methyl-pyridineamine (Kress, T. J.; Moore, L. L.; Costantino, S. M. J. Org. Chem. (1976) 41(1), pp 93-96) in 1 L of dichloromethane was added 164 g (666 mmol) of m-chloroperoxybenzoic acid. The mixture was stirred at room temperature overnight and 20 g more of m-chloroperoxybenzoic acid was added. The mixture was stirred 1 h and 50 mL of saturated aqueous NaHSO₃ were added. The solvent was removed and the residue was taken up in 1L of 1N HCl. The insoluble solids were filtered and washed with 3N HCl. Solvent was removed from the aqueous filtrate to give a solid which was recrystallized from ethanol affording 56.9 g of 5-chloro-6-methyl-2-pyridinamine 1-oxide, hydrochloride as a white solid, mp>250° C.

Step F: Preparation of 4-chloro-1-hydroxy-5-methyl-1H-pyrrole-2-carbonitrile

A solution of 55.9 g (287 mmol) of 5-chloro-6-methyl-2-pyridinamine-1-oxide, hydrochloride in 1 L 10% aq HCl was cooled to 0° C. An aqueous solution of 25.5 g (365 mmol) of sodium nitrite was added dropwise. After stirring 15 min, an aqueous solution of 23.7 g (365 mmol) sodium azide was added dropwise. The mixture was stirred at room temperature overnight then extracted 3 times with methylene chloride. Drying (MgSO₄) and removal of solvent gave 35 g of an orange solid which was dissolved in chloroform and heated at reflux for 4 days. Removal of solvent gave product which was purified by chromatography on silica gel (CH₂Cl₂ followed by ether) to isolate 2 components: 4.8 g of a higher R_(f) material identified as 4-chloro-5-methyl-1H-pyrrole-2-carbonitrile. ¹H NMR (CDCl₃) δ 2.3 (s, 3H), 6.7 (s, 1H), 8.9 (br s, 1H) and 17.8 g of 4-chloro-1-hydroxy-5-methyl-1H-pyrrole-2-carbonitrile, mp 91-101° C., ¹H NMR (CDCl₃) 62.25 (s, 3H), 6.5 (s, 1H).

Step G: Preparation of (R)-4-chloro-1-[2-(1,3-dihydro-1.3-dioxo-2H-isoindol-2-yl)propoxy]-5-methyl-1H-pyrrole-2-carbonitrile

A solution of 3.0 g (10.6 mmol) of(R)-2-[1-methyl-2-[(methylsulfonyl)oxy]ethyl]-1H-isoindole-1,3(2H)-dione, 2.0 g (12.7 mmol) of N-chloro-1-hydroxy-5-methyl-1H-pyrrole-2-carbonitrile and 1.76 g (12.7 mmol) of K₂CO₃ in 60 mL acetonitrile was heated at reflux overnight. Solvent was removed and the residue was taken up in ethyl acetate which was washed with water and brine. Drying (MgSO₄) and removal of solvent gave an oil which was chromatographed on silica gel (35% ether in hexanes) to give 2.55 g of (R)-4-chloro-1-[2-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)propoxy]-5-methyl-1H-pyrrole-2-carbonitrile as a white solid, ¹H NMR (CDCl₃) δ 1.55 (d, 3H), 2.15 (s, 3H), 4.45 (m, 1H), 4.8 (m, 2H), 6.5 (s, 1H), 7.75 (m, 2H), 7.85 (m, 2H).

Step H: Preparation of (R)-1-(2-aminopropoxy)-4-chloro-5-methyl-1-1H-pyrrole-2-carbonitrile

A solution of 0.6 g (1.75 mmol) of (R)-4-chloro-1-[2-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)propoxy]-5-methyl-1H-pyrrole-2-carbonitrile and 0.42 mL (8.7 mmol) of hydrazine was heated at reflux for 50 min and cooled to room temperature. Precipitated solids were filtered and rinsed with ether. Solvent from the filtrate was removed and the residue was taken up in ether. The insoluble solids were filtered and rinsed with ether. The filtrate was stripped to afford 0.43 g of (R)-1-(2-aminopropoxy)-4-chloro-5-methyl-1-1H-pyrrole-2-carbonitrile as an oil.

Step 1: Preparation of [1R-[1α(R*),3α]]-2,2-dichloro-N-[2-[(3-chloro-5-cyano-2-methyl-1H-pyrrol-1-yl)oxy]-1-methylethyl]-1-ethyl-3methylcyclopropanecarboxamide mixed 1:1 with [1S-[1α(S*),3β]]-2,2-dichloro-N-[2-[(3-chloro-5-cyano-2-methyl-1H-pyrrol-1-yl)oxy]-1-methylethyl]-1-ethyl-3-methylcyclopropanecarboxamide

In a separate flask, 0.34 g (1.75 mmol) of (trans)-2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid in 15 mL thionyl chloride was heated at reflux for 30 min. The thionyl chloride was stripped and the residue was dried in vacuo. The residue was dissolved in 20 mL methylene chloride and a solution of 0.43 g of (R)-1-(2-aminopropoxy)-4-chloro-5-methyl-1H-pyrrole-2-carbonitrile and 0.25 mL (1.8 mmol) triethylamine was added dropwise. The mixture was stirred at room temperature overnight. Solvent was stripped and the residue was taken up in ethyl acetate which was washed with water and brine. Drying (MgSO₄) and removal of solvent gave an oil which was chromatographed (40% ether in hexanes) on silica gel to give the title compounds as a 1:1 mixture of diastereomers as an oil, ¹H NMR (CDCl₃) δ 1.0 (m, 3H), 1.2 (d, 3H), 1.4 (2d, 3H, 1:1 ratio), 1.5-1.65 (m, 1H), 2.0-2.2 (m, 1H), 2.2 (s, 3H), 2.2-2.3 (m, 1H), 4.2-4.4 (m, 2H), 4.4-4.6 (m, 1H), 6.05 and 6.15 (2d, 1H, 1:1 ratio), 6.55 (2s, 1H, 1:1 ratio).

EXAMPLE 3

Step A: Preparation of 1,1-dimethylethyl[2-(2-cyano-4-fluorophenoxy)-1-methylethyl]carbonate

Sodium hydride (1.26 g of a 60% dispersion in oil, 31.5 mmol) was rinsed 3 times with hexanes and suspended in 30 mL DMF at 5° C. Added was 4.5 mL (49.6 mmol) of 2,5-difluorobenzoritrile followed by 5.0 g (28.6 mmol) of (2-hydroxy-1-methylethyl)-carbamic acid-1,1-dimethylethyl ester portionwise. The mixture was stirred at room temperature overnight before being quenched with saturated aqueous NH₄Cl. After partitioning between ether and water, the ether was separated and washed 2 times with water and with brine. Drying (MgSO₄) and removal of solvent gave a solid which was triturated with hexanes to give 6.3 g of 1,1-dimethylethyl[2-(2-cyano-4-fluorophenoxy)-1-methylethyl]carbamate as a white solid, mp 77-78° C.

Step B: Preparation of 2-(2-aminopropoxy)-5-fluorobenzonitrile

A solution of 1.0 mL trifluoroacetic acid and 1.2 g (4.08 mmol) of 1,1-dimethylethy][2-(2-cyano-4-fluorophenoxy)-1-methylethyl]carbamate in 10 mL methylene chloride was stirred at ambient temperature for 3 days. Solvent was removed and the residue was taken up in aqueous Na₂CO₃ and ethyl acetate. The organic layer was separated and washed with water and brine. Drying (MgSO₄) and removal of solvent gave 650 mg of 2-(2-aminopropoxy)-5-fluorobenzonitrile as an oil.

Step C: Preparation of (trans)-2,2-dichloro-N-[2-(2-cyano-4-fluorophenoxy-1-methylethyl]-1-ethyl-3-methylcyclopropanecarboxamide

In a separate flask, 750 mg (3.8 mmol) of (trans)-2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid in 20 mL thionyl chloride was heated at reflux for 30 min. The thionyl chloride was stripped and the residue was dried in vacuo. The residue was then dissolved in 20 mL methylene chloride and a solution of 0.67 g (3.45 mmol) 2-(2-aminopropoxy)-5-fluorobenzonitrile and 0.55 mL (3.95 mmol) triethylamine was added dropwise. The mixture was stirred at room temperature overnight. Solvent was stripped and the residue was taken up in ethyl acetate which was washed with water and brine. Drying (MgSO₄) and removal of solvent gave an oil which was chromatographed (50% ether in hexanes) on silica gel to give the title compound as a 1:1 mixture of diastereomers, mp 119-123° C. ¹H NMR (CDCl₃) δ 0.9 and 0.95 (2t, 3H, 1:1 ratio), 1.2 (d, 3H), 1.45 (m, 3H), 1.5-1.6 (m, 1H), 2.0-2.1 (m, 1H), 2.2 (m, 1H), 4.0-4.2 (m, 2H), 4.45 (m, 1H), 6.95 (m, 1H), 7.3 (m, 2H).

EXAMPLE 4

Step A: Preparation of 2-[1-methyl-2-[(methylsulfonyl)oxy]propyl]-1H-isoindole-1,3(2H)-dione

Methanesulfonyl chloride (9.7 mL, 56 mmol) was added to a solution of 10.5 g (48 mmol) of 2-(2-hydroxy-1-methylpropyl)-1H-isoindole-1,3(2H)-dione (JP 01242569 A2) and 8.1 mL (58 mmol) of triethylamine and the mixture was stirred at room temperature overnight. The mixture was diluted with ether and washed with water and brine. Drying (MgSO₄) and removal of solvent gave an oil which slowly solidified. Trituration with hexanes gave 11.8 g of 2-[1-methyl-2-[(methylsulfonyl)oxy]propyl]-1H-isoindole-1,3(2H)-dione as a white solid, mp 67-73° C.

Step B: Preparation of 4-chloro-1-[3-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)butyl]-5-methyl-1H-pyrrole-2-carbonitrile

A solution of 4.23 g (14.2 mmol) of 2-[1-methyl-2-[(methylsulfonyl)oxy]propyl]-1H-isoindole-1,3(2H)-dione, 2.05 g (14.2 mmol) of 4-chloro-5-methyl-1H-pyrrole-2-carbonitrile and 2.35 g (14.2 mmol) of K₂CO₃ in 60 mL DMF was heated at 60° C. overnight. The mixture was diluted with ether and washed 4 times with water. Drying (MgSO₄) and removal of solvent gave an oil which was chromatographed on silica gel (15% ethyl acetate in hexanes) to give 3.2 g of 4-chloro-1-[3-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)butyl]-5-methyl-1H-pyrrole-2-carbonitrile as a solid, ¹NMR (CDCl₃) δ 1.5 (d, 3H), 2.2 (s, 3H and m, 1H), 2.7 (m, 1H), 3.9 (m, 1H), 4.05 (m, 1H), 4.4 (m, 1H), 6.6 (s, 1H), 7.85 (m, 2H), 7.9 (m, 2H).

Step C: Preparation of 1-(3-aminobutyl)-4-chloro-5-methyl-1H-pyrrole-2-carbonitrile

A solution of 3.2 g (9.4 mmol) of 4-chloro-1-[3-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)butyl]-5-methyl-1H-pyrrole-2-carbonitrile and 4.8 mL (94 mmol) of hydrazine in ethanol was heated at reflux for 60 min and cooled to room temperature. Precipitated solids were filtered and rinsed with ethyl acetate and the filtrate was concentrated to afford 1-(3-aminobutyl)-4-chloro-5-methyl-1H-pyrrole-2-carbonitrile as an oil.

Step D: Preparation of 2-cyano-3,4,4-trimethylpentanoic acid

A solution of 10 g (50 mmol) of ethyl 2-cyano-3,4,4-trimethylphenanote (Clarke, N. C.; Runciman, P. J. I.; Utley, J. H. P.; Landquist, J. K. J. Chem. Soc., Perkin Trans. 2 (1987) (4), pp 435-439) and 2.93 g (52 mmol) of potassium hydroxide in 50 mL ethanol was heated at reflux for 3 h and stirred at room temperature overnight. The mixture was diluted with water and extracted twice with ether. The aqueous layer was acidified with concentrated HCl and extracted twice with ether which was washed with brine, dried (MgSO₄) and concentrated to afford 9.6 g of 2-cyano-3,4,4-trimethylpentanoic acid as a mixture of diastereomers, mp 68-78° C.

Step E: Preparation of N-[3-(3-chloro-5-cyano-2-methyl-1H-pyrrol-1-yl)-1-methylpropyl]-2-cyano-3,4,4-trimethylpentanamide

A solution of 0.54 g (3.5 mmol) 2-cyano-3,4,4-trimethylpentanoic acid in 15 mL thionyl chloride was heated at reflux for 30 min. The thionyl chloride was stripped and the residue was dried in vacuo. The residue was then dissolved in 20 mL methylene chloride and a solution of 0.66 g (3.13 mmol) of 1-(3-aminobutyl)-4-chloro-5-methyl-1H-pyrrole-2-carbonitrile and 0.59 mL (4.2 mmol) triethylamine was added dropwise. The mixture was stirred at room temperature overnight. Solvent was stripped and the residue was taken up in ethyl acetate which was washed with water and brine. Drying (MgSO₄) and removal of solvent gave an oil which was chromatographed (40% ether in hexanes) on silica gel to give the title compound as a mixture of diastereomers, mp 111-118° C. ¹H NMR (CDCl₃) δ 1.0 (m, 3H), 1.2-1.3 (2m, 6H), 1.4 (d, 1H), 1.6 (m, 2H), 1.9 (m, 2H), 2.2 (m, 3H), 4.1 (2m, 2H), 5.7 (in, 1H), 6.65 (2s, 1H).

EXAMPLE 5

Step A: Preparation of bis(1,1-dimethylethyl)-1-propenylimidodicarbonate

A solution of commercially available di-tert-butyliminodicarboxylate (25.0 g, 0.115 mol) in 100 mL of tetrahydrofuran was added to hexanes rinsed sodium hydride (5.0 g of 60% oil suspension, 0.125 mol) and stirred for 3 h at 20° C. A solution of allyl bromide ((12.0 mL, 0.139 mol) in 30 mL tetrahydrofuran was added dropwise and the mixture was stirred 20 h. The reaction was quenched dropwise with 10 mL water, evaporated to a paste, treated with 200 mL water and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated solution of ammonium chloride then concentrated to give an oil. The oil was purified by flash silica chromatography using 5% ethyl acetate/hexanes solution as eluent to give 26.0 g (88%) of bis(1,1-dimethylethyl)-1-propenylimidodicarbonate as colorless crystals: mp 44-46° C.; ¹H NMR (300 MHz, CDCl₃) δ 1.50 (s, 18H), 4.18 (m, 2H), 5.14 (m, 2H), 6.85 (m, 1H).

Step B: Preparation of bis(1,1-dimethylethyl)-2-propenyl-3-(2-fluorophenyl)imidodicarboxylate

A solution of bis(1,1-dimethylethyl)-2-propenylimidodicarbonate (7.00) g, 27 mmol) and o-fluoroiodobenzene (8.10 g, 36.5 mmol) in 40 mL acetoritrile was treated with triphenylphosphine (2.2 g, 8.4 mmol), tetrabutylammonium chloride (5.30 g, 18.3 mmol), potassium carbonate (12.4 g, 89.7 mmol) and palladium acetate (0.640 g, 2.85 mmol). The reaction mixture was heated at 65° C. for 4 h then treated with more palladium acetate (0.320 g, 1.43 mmol). The reaction mixture was stirred an additional 20 h at 65° C. The solvent was evaporated and the residue was purified by flash chromatography using 5% ethyl acetate/hexanes solution as eluent to give 4.0 g (42%) of bis(1,1-dimethylethyl)-2-propenyl-3-(2-fluorophenyl)imidodicarboxylate as a light yellow oil: ¹H NMR (CDCl₃) δ 1.52 (s, 18H), 4.36 (d, 2H), 6.30 (dt, 1H), 6.70 (d, 1H), 7.10 (m, 2H), 7.20 (m, 1H), 7.40 (t, 1H).

Step C: Preparation of (trans)-3-(2-fluorophenyl)-2-propen-1-amine hydrochloride

A solution of bis(1,1-dimethylethyl)-2-propenyl-3-(2-fluorophenyl) imidodicarboxylate (4.0 g, 11 mmol) in 30 mL of methylene chloride and 15 mL of trifluoroacetic acid was stirred at 20° C. for 18 h. The reaction mixture was evaporated and the residue diluted in ethyl acetate and washed twice with 1 N sodium hydroxide solution. Organic layer was evaporated to give the crude amine. Free amine was precipitated with hydrogen chloride (1 N in diethyl ether) and filtered through a fritted funnel to give 2.42 g (91%) of (trans)-3-(2-fluorophenyl)-2-propen-1-amine hydrochloride as a white powder: mp 205-208° C.; ¹H NMR (Me₂SO-d₆) δ 3.66 (d, 2H), 6.40 (dt, 1H), 6.81 (d, 1H), 7.24 (m, 2H), 7.40 (m, 1H), 7.60 (m, 1H), 8.20 (br s, 3H).

Step D: Preparation of (trans)-2,2-dichloro-1-ethyl-N-[3-(2-fluororphenyl)-2-propenyl]-3-methylcyclopropanecarboxamide

A solution of (trans)-2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid (see above) (5.1 g, 25.9 mmol) and 40 mL of toluene was treated with thionyl chloride (5.0 mL, 69 mmol) and warmed at 65° C. for 3 h. The solvent was evaporated and the residue was diluted in 5% toluene/Hexanes and treated with activated carbon. The suspension was filtered and the filtrate was concentrated in vacuo to give 5.05 g (91%) of the (trans)-2,2-dichloro-1-ethyl-3-methylcyclopropanecarbonyl chloride as a clear oil. A solution of acid chloride (0.33 g, 1.53 mmol) in 10 mL methylene chloride was added dropwise to a solution of amine of (trans)-3-(2-fluorophenyl)-2-propen-1-amine hydrochloride (0.40 g, 2.1 mmol), triethyl amine (1.0 mL, 7.2 mmol) in 30 mL methylene chloride. The reaction mixture was stirred for 2 h then concentrated in vacuo. The residue was purified by flash chromatography using 10% ethyl acetate/hexanes as eluent to give 0.480 g (95%) of the title compound as white solid: mp 103-105° C, ¹H NMR (CDCl₃) δ 1.01 (t, 3H), 1.25 (m, 3H), 1.60 (m, 1H), 2.00 (m, 1H), 2.22 (m, 1H), 4.11 (m, 2H), 5.90 (br s, 1H), 6.30 (dt, 1H), 6.75 (d, 1H), 7.07 (m, 2H), 7.20 (m, 1H), 7.40 (t, 1H).

EXAMPLE 6

Step A: Preparation of 2-[2-(2-ethylphenoxy)-1-methylethyl]-1H-isoindole-1,3(2H-dione

A solution of 5.0 g (24.4 mmol) of 2-(2-hydroxy-1-methylethyl)-1H-isoindole-1,3(2H)-dione (Y. Becker, A. Eisenstadt, J. K. Stille, J. Org. Chem., 1980, 45, 2145) and triphenylphosphine (7.00 g, 27.0 mmol) in 40 mL of dry tetrahydrofuran was stirred at 20° C. for 1 h. To the solution was added 2-ethylphenol (3.90 g, 32.0 mmol) and diethyl azodicarboxylate (5.0 mL, 32.0 mmol) and the solution was stirred an additional 40 h. The reaction mixture was concentrated in vacuo and the residue was diluted in diethyl ether and washed with water and brine. The organic layer was concentrated in vacuo and the crude product was purified by flash silica chromatography using 5% ethyl acetate/hexanes solution as eluent to give 3.0 g (40%) of 2-[2-(2-ethylphenoxy)-1-methylethyl]-1H-isoindole-1,3(2H)-dione as a colorless oil: ¹H NMR (CDCl₃) δ 0.96 (t, 3H), 1.60 (d, 3H), 2.40 (m, 2H), 4.18 (dd, 1H), 4.48 (t, 1H), 4.84 (m, 1H), 6.80 (m, 1H), 6.90 (m, 1H), 7.10 (m, 2H), 7.70 (m, 2H), 7.84 (m, 2H).

Step B: Preparation of 1-(2-ethylphenoxy)propanamine hydrochloride

2-[2-(2-Ethylphenoxy)-1-methylethyl]-1H-isoindole-1,3(2H)-dione (3.0 g, 9.7 mmol) was dissolved in 300 mL of absolute ethanol and treated with anhydrous hydrazine (3.0 mL, 96 mmol) at reflux for 2 h. Reaction mixture was cooled and filtered through a fritted funnel and then the filtrate was concentrated. The residue was diluted in ethyl acetate and filtered mixture through a fritted funnel. The organic layer was extracted twice with 1 N hydrogen chloride solution. Aqueous layer was treated with 1 N sodium hydroxide solution (until solution pH=8-10), and was then extracted with ethyl acetate. The final organic layer was concentrated in vacuo to give 1-methyl-2-(2-fluorophenoxy)ethylamine as an oil. Free amine was precipitated with hydrogen chloride (1 N in diethyl ether) and filtered via a fritted funnel to give 1.30 g (62%) of 1-(2-ethylphenoxy)propanamine hydrochloride as a white powder: mp 131-133° C.; ¹H NMR (Me₂SO-d₆) δ 1.18 (t, 3H), 1.40 (d, 3H), 2.75 (m, 1H), 3.62 (m, 1H), 4.10 (m, 2H), 6.95 (m, 2H), 7.20 (m, 2H), 8.25 (br s, 3H).

Step C: Preparation of 2-cyano-N-[2-(2-ethylphenoxy)-1-methylethyl]-3,3-dimethylbutanamide

A solution of 2-cyano-3,3-dimethylbutanoyl chloride (E. Schaumann, H. Mrotzek; J. Org. Chem., 1979, 35, 1965) (0.364 g, 2.28 mmol) in 10 mL methylene chloride was added dropwise to a solution of 1-(2-ethylphenoxy)propanamine hydrochloride (0.56 g, 2.6 mmol), triethyl amine (1.0 mL, 7.2 mmol) in 30 mL methylene chloride. The reaction mixture was stirred for 2 h then concentrated in vacuo. The residue was purified by flash chromatography using 20% ethyl acetate/hexanes as eluent to give 0.290 g (42%) of the title compound as a white solid: mp 94-97° C., ¹H NMR (CDCl₃) δ 1.20 (m, 12H), 1.40 (m, 3H), 2.65 (q, 2H), 3.16 (dd, 1H), 3.98 (m, 1H), 4.05 (m, 1H), 4.40 (m, 1H), 6.00 (d, 1H), 6.25 (dd, 1H), 6.95 (t, 1H), 7.18 (t, 2H).

EXAMPLE 7

Step A: Preparation of 2-fluoro-3-methyl-2-butenyl cyanoacetate

A solution of cyano acetic acid (2.25 g, 26.4 mmol) in 30 mL dry CH₂Cl₂ was cooled in ice water before 2.3 mL (26.4 mmol) of oxalyl chloride and 3 drops of DMF were added. The mixture was warmed to room temperature with stirring overnight before being added dropwise to an ice-cooled solution of 2.5 g (24 mmol) of 2-fluoro-4-methyl-2-buten-1-ol (Cane, D. E.; Yang, G.; Xue, Q.; Shin, J. H. Biochemistry (1995), 3418, 2471-9) and 3.7 mL (26.4 mmol) triethylamine. After stirring 3 h at room temperature, solvent was removed and the residue was partitioned between water and ether. The ether layer was separated and washed with brine. The combined aqueous washings were extracted with ether which was washed with brine. The combined ether extracts were dried (MgSO₄), and solvent was removed to afford 3.5 g of the title compound of Step A as an oil, ¹H NMR (CDCl₃) δ 1.7 (m, 6H), 3.5 (s, 2H), 4.85 (d, J=22 Hz, 2H).

Step B: Preparation of 2-cyano-4-fluoro-3,3-dimethyl-4-pentenoic acid

A solution of (3.5 g, 20.5 mmol) the product from Example 7, Step A in 25 mL hexamethyldisilazane was heated at reflux for 2 h. Solvent was removed and the residue was dissolved in 50 mL 1N HCl. The mixture was heated at reflux for 20 min. After cooling, the mixture was extracted with ether which was washed with brine and dried (MgSO₄). Removal of solvent gave 3.2 g of the title compound of Step B as an oil, ¹H NMR (CDCl₃) δ 1.4 (s, 3H), 1.45 (s, 3H), 3.8 (s, 1 H), 4.55 (d of d, J=50, 4 Hz, 1H), 4.75 (d of d, J=25, 1 Hz, 1H), 6.5 (br s, 1H).

Step C: Preparation of (R)-2-[2-(2,5-difluorophenoxyl-1-methylethyl]-1H-isoindole-1,3(2H)-dione

A solution of 15.8 g (77 mmol) of(R)-2-(2-hydroxy-1-methylethyl)-1H-isoindole-1,3(2h)-dione, 24.2 g (92 mmol) of triphenylphosphine and 10.0 g (77 mmol) of 2,5-difluorophenol was stirred while 18.2 mL (116 mmol) of diethylazodicarboxylate was added dropwise. After stirring at ambient temperature overnight, solvent was removed and the residue was dissolved in ethyl acetate. The ethyl acetate was washed with water and brine. Drying (MgSO₄) and removal of solvent gave an oil which was chromatographed on silica gel to give 15.6 g of the title compound of Step C as an oil, ¹H NMR (CDCl₃) δ1.55 (d. 3H), 4.25 (m, 1H), 4.8 (m, 1H), 6.55 (m, 1H), 6.65 (m, 1H), 6.9 (m, 1H), 7.7 (m, 2H), 7.85 (m, 2H).

Step D: Preparation of 1-(2,5-difluorophenoxy)proponamine hydrochloride

A solution of 15.6 g (44.2 mmol) of (R)-2-[2-(2,5-difluorophenoxy-1-methylethyl]-1H-isoindole-1,3(2H)-dione and 7.7 mL of anhydrous hydrazine in 400 mL ethanol was heated at reflux for 2 h. Solids were filtered and rinsed with ethyl acetate. Solvent was removed and the residue was partitioned between ether and 1N HCl (aq). The aqueous layer was separated, basified with 50% sodium hydroxide and extracted with ether. The ether was washed with brine and dried (MgSO₄). After removal of solvent, the residue was redissolved in ether and 45 mL of 1N HCl in ether was added to form the hydrochloride salt precipitate. The precipitate was filtered and rinsed with ether affording 8.5 g of the title compound of Step D as a white solid, mp 127-129° C.

Step E: Preparation of [R-(R*,R*)]-2-cyano-N-[2-(2,5-difluorophenoxy)-1-methylethyl]-4-fluoro-3,3-dimethyl-4-pentenamide mixed 1:1 with [R-(R*S*)]-2-cyano-N-[2-(2,5-difluorophenoxyl-1-methylethyl]-4-fluoro-3,3-dimethyl-4-pentenamide

A solution of 370 mg (2.16 mmol) of the acid from Step A, 0.19 mL (2.15 mmol) oxalyl chloride and 2 drops DMF in 10 mL CH₂Cl₂ was stirred at room temperature overnight. This mixture was added to a solution of 400 mg (1.8 mmol) of the amine salt of Step D and 0.52 mL (3.7 mmol) triethylamine in 10 mL CH₂Cl₂. After stirring overnight, 0.3 g Amberlite IRA-78 resin was added and the mixture was filtered through silica gel, rinsing through with ethyl acetate. The filtrate was concentrated to give 570 mg of the title compound of Step E as a solid, mp 106-110° C.

EXAMPLE 8

Step A: Preparation of [R-(E)]-phenylmethyl [3-(2,5-difluorophenyl-1-methyl-2-propenyl]carbamate

A solution of 4.0 g (21 mmol) of (R)-phenylmethyl 2-methyl-1-azimidinecarboxylate (Deilaria, J. F. Jr.; Sallin, K. J. Tetrahedron Leut. (1990), 31, 2661), 5.0 g (35 mmol) of 2,5-difluorobenzaldehyde (Aldrich) and 6.5 g (26 mmol) of triphenylphosphine (Aldrich) in 100 mL isopropyl alcohol was heated at reflux for 4 h. The mixture was cooled to 22° C. and stirred 20 h. The reaction mixture was concentrated to an oil then purified by flash silica chromatography (5% ethyl acetate in hexanes) to give 4.0 g of title compound of Step A as a 4 to 5 mixture of cis to trans isomers as a white solid mp 82-84° C., ¹H NMR (CDCl₃) trans isomer: δ 7.35 (m, 5H), 7.10 (m, 1H), 6.95 (m, 2H), 6.60 (d, 1H), 6.25 (dd, 1H), 5.12 (s, 2H), 4.80 (m, 1H), 4.60 (m, 1H), 1.36 (d, 3H); cis isomer: δ 7.35 (m, 5H), 7.10 (m, 1H), 6.95 (m, 2H), 6.40 (d, 1H), 5.65 (dd, 1H), 5.07 (s, 2H), 4.80 (m, 1H), 4.60 (m, 1H), 1.27 (d, 3H).

Step B: Preparation of [R-(E)]-4-(2,5-difluorophenyl)-3-buten-2-amine hydrochloride

In a small flask, 3.1 g (9.8 mmol) of the product of Example 8, Step A was treated with 8 mL of 30% hydrogen bromide in acetic acid. The reaction mixture was stirred at 22° C. for 8 h. Diluted reaction mixture with 200 mL ethyl acetate then washed twice with 100 mL of 1N sodium hydroxide, then once with 50 mL brine. Extracted the ethyl acetate layer twice with 100 mL of 1N HCl. Treated the acidic aqueous layer with 250 mL of 1N sodium hydroxide. Then extracted this solution with ethyl acetate. Concentrated this final organic layer to give the free amine as an oil. Diluted the free amine oil in 100 mL of dry ether then treated with 20 mL of 1N HCl in ether. A white precipitate was filtered and dried to give 1.0 g of title compound of Step B as a 3 to 7 mixture of cis to trans isomers. Amine salt is a white solid, mp 133-136° C., ¹H NMR ((CH₃)₂SO-d₆) trans isomer: δ 8.30 (br s, 3H), 7.50 (m, 1H), 7.30 (m, 2H), 6.80 (d, 1H), 6.50 (dd, 1H), 4.00 (m, 1H), 1.39 (d, 3H); cis isomer: δ 8.30 (br s, 3H), 7.50 (m, 1H), 7.30 (m, 2H), 6.62 (d, 1H), 5.90 (t, 1H), 4.00 (m, 1H), 1.31 (d, 3H).

Step C: Preparation of [1[R-(E)]-trans]-2,2-dichloro-N-[3-(2,5-difluorophenyl) 1-methyl-2-propenyl]-1-ethyl-3-methylcyclopropanecarboxamide

In a separate flask 0.50 g (2.5 mmol) of (trans)-2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxlic acid in 20 mL thionyl chloride was heated at reflux for 30 min. The reaction mixture was concentrated and the residue was dried in vacuo. The crude acid chloride was diluted in 20 mL of methylene chloride and added dropwise to a solution of 0.42 g (1.9 mmol) of [R-(E)]-4-(2,5-difluorophenyl)-3-buten-2-amine hydrochloride and 1.0 mL (7.1 mmol) of triethylamine in 20 mL of methylene chloride. The reaction mixture was stirred at 22° C. for 2 h then diluted with 100 mL methylene chloride and washed with 100 mL in HCl. The organic layer was concentrated to an oil. The crude amide was purified by flash silica chromatography using 20% ethyl acetate in hexanes as eluent to give 130 mg of a less polar trans isomer as an oil. ¹H NMR (CDCl₃) δ7.10 (m, 1H), 6.95 (m, 2H), 6.65 (d, 1H), 6.30 (dd, 1H), 5.80 (br s, 1H), 4.05 (m, 1H), 2.20 (q, 1H), 2.00 (m, 1H), 1.60 (m, 1H), 1.40 (d, 3H), 1.20 (d, 3H), 1.00 (t, 3H) and 140 mg of a more polar trans isomer as a white solid, mp 102-105° C., ¹H NMR (CDCl₃) δ 7.10 (m, 1H), 6.95 (m, 2H), 6.70 (d, 1H), 6.28 (dd, 1H), 5.80 (br s, 1H), 4.85 (m, 1H), 2.23 (q, 1H), 2.00 (m, 1H), 1.60 (m, 1H), 1.40 (d, 3H), 1.20 (d, 3H), 1.00 (t, 3H).

By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 9 can be prepared. The following abbreviations are used in the Tables which follow: t tertiary, n=normal, i=iso, C=cyclo, F=fluorine, Br=bromine, Cl=chlorine, I=iodine, Me=methyl, Et=ethyl, Pr=propyl, i-Pr=isopropyl, Bu=butyl, Ph=phenyl, CF₃=trifluoromethyl, SCF₃=trifluoromethylthio, CN=cyano and SiMe₃=trimethylsilyl. TABLE 1

Z = Column 1 Column 2 Column 3 1 C₆H₅ 2-n-Pr-6-CN-C₆H₃ 2-CF₃-1H-pyrrol-1-yl 2 2-F-C₆H₄ 2-Cl-5-F-C₆H₃ 2,3-diCl-1H-pyrrol-1-yl 3 3-F-C₆H₄ 2-F-3-Me-C₆H₃ 2,4-diCl-1H-pyrrol-1-yl 4 4-F-C₆H₄ 2-F-5-Me-C₆H₃ 3,4-diCl-1H-pyrrol-1-yl S 2-Cl-C₆H₄ 3-F-6-Me-C₆H₃ 2,3-diBr-1H-pyrrol-1-yl 6 3-Cl-C₆H₄ 2-thienyl 2,4-diBr-1H-pyrrol-1-yl 7 4-Cl-C₆H₄ 3-F-2-thienyl 4-F-5-Br-1H-pyrrol-1-yl 8 2-Br-C₆H₄ 4-F-2-thienyl 2-Cl-3-Br-1H-pyrrol-1-yl 9 3-Br-C₆H₄ 5-Et-2-thienyl 2-Cl-4-Br-1H-pyrrol-1-yl 10 4-Br-C₆H₄ 3-Cl-2-thienyl 3-Cl-4-Br-1H-pyrrol-1-yl 11 2-I-C₆H₄ 4-Cl-2-thienyl 3-Cl-5-Br-1H-pyrrol-1-yl 12 3-I-C₆H₄ 5-Cl-2-thienyl 4-F-5-Me-1H-pyrrol-1-yl 13 4-I-C₆H₄ 3-(C≡CH)-2-thienyl 2-Cl-3-Me-1H-pyrrol-1-yl 14 2-Me-C₆H₄ 4-Br-2-thienyl 2-Cl-4-Me-1H-pyrrol-1-yl 15 3-Me-C₆H₄ 5-Br-2-thienyl 2-Cl-5-Me-1H-pyrrol-1-yl 16 4-Me-C₆H₄ 3-(CH≡CH₂)-2-thienyl 3-Cl-4-Me-1H-pyrrol-1-yl 17 2-Et-C₆H₄ 3,4-diF-2-thienyl 3-Cl-5-Me-1H-pyrrol-1-yl 18 2-CN-C₆H₄ 3-F-5-Br-2-thienyl 4-Cl-5-Me-1H-pyrrol-1-yl 19 2-CF₃-C₆H₄ 4-F-5-Br-2-thienyl 2-Br-3-Me-1H-pyrrol-1-yl 20 2-n-Pr-C₆H₄ 3-Br-4-F-2-thienyl 2-Br-4-Me-1H-pyrrol-1-yl 21 2-i-Pr-C₆H₄ 3-Br-5-F-2-thienyl 2-Br-5-Me-1H-pyrrol-1-yl 22 2-n-Bu-C₆H₄ 4-Br-5-F-2-thienyl 3-Br-4-Me-1H-pyrrol-1-yl 23 2-SiMe₃-C₆H₄ 3-F-4-Me-2-thienyl 3-Br-5-Me-1H-pyrrol-l-yl 24 2-CH₂F-C₆H₄ 3-F-5-Me-2-thienyl 4-Br-5-Me-1H-pyrrol-1-yl 25 3-CH₂F-C₆H₄ 4-F-5-Me-2-thienyl 2-n-Pr-3-F-1H-pyrrol-1-yl 26 2-CH₂CN-C₆H₄ 3-Me-4-F-2-thienyl 2-n-Pr-4-F-1H-pyrrol-1-yl 27 2-CH₂CH₂F-C₆H₄ 3-Me-5-F-2-thienyl 2-n-Pr-5-F-1H-pyrrol-1-yl 28 2-(CH═CH₂)-C₆H₄ 4-Me-5-F-2-thienyl 2-n-Pr-3-Cl-1H-pyrrol-1-yl 29 2-(CH₂CH═CH₂)-C₆H₄ 3-Me-5-Cl-2-thienyl 2-n-Pr-4-Cl-1H-pyrrol-l-yl 30 2-(CH═CHCN)-C₆H₄ 3-Br-5-Me-2-thienyl 2-n-Pr-5-Cl-1H-pyrrol-1-yl 31 2-(C-CH)-C₆H₄ 3-Me-5-Br-2-thienyl 2-n-Pr-3-Br-1H-pyrrol-1-yl 32 2-(CH₂C-CH)-C₆H₄ 4-Me-5-Br-2-thienyl 2-n-Pr-4-Br-1H-pyrrol-1-yl 33 2-(C-CMe)-C₆H₄ 3-n-Pr-4-F-2-thienyl 2-n-Pr-5-Br-1H-pyrrol-1-yl 34 2-(t-Bu)-C₆H₄ 3-n-Pr-5-F-2-thienyl 2-n-Pr-3-Me-1H-pyrrol-1-yl 35 2-[CH(F)Me]-C₆H₄ 3-CN-5-Br-2-thienyl 2-n-Pr-4-Me-1H-pyrrol-1-yl 36 2,3-diF-C₆H₃ 3-thienyl 2-n-Pr-5-Me-1H-pyrrol-1-yl 37 2,4-diF-C₆H₃ 2-F-3-thienyl 2-CN-3-F-1H-pyrrol-1-yl 38 2,5-diF-C₆H₃ 4-F-3-thienyl 2-CN-4-F-1H-pyrrol-l-yl 39 2,6-diF-C₆H₃ 5-F-3-thienyl 2-CN-5-F-1H-pyrrol-1-yl 40 3,4-diF-C₆H₃ 2-Cl-3-thienyl 2-CN-3-Cl-1H-pyrrol-1-yl 41 3,5-diF-C₆H₃ 4-Cl-3-thienyl 2-CN-4-Cl-1H-pyrrol-l-yl 42 2,3-diCl-C₆H₃ 5-Cl-3-thienyl 2-CN-5-Cl-1H-pyrrol-1-yl 43 2,4-diCl-C₆H₃ 2-CN-3-thienyl 2-CN-3-Br-1H-pyrrol-1-yl 44 2,5-diCl-C₆H₃ 5-CN-3-thienyl 2-CN-4-Br-1H-pyrrol-1-yl 45 2,6-diCl-C₆H₃ 2-Br-3-thienyl 2-CN-5-Br-1H-pyrrol-1-yl 46 3,4-diCl-C₆H₃ 5-Br-3-thienyl 2-CN-3-Me-1H-pyrrol-1-yl 47 3,5-diCl-C₆H₃ 2-n-Pr-3-thienyl 2-CN-4-Me-1H-pyrrol-1-yl 48 2,5-diBr-C₆H₃ 2-(CH₂CN)-3-thienyl 2-CN-5-Me-1H-pyrrol-1-yl 49 2-Br-5-Cl-C₆H₃ 2,5-diCl-3-thienyl 2-CN-5-n-Pr-1H-pyrrol-1-yl 50 3-Br-6-Cl-C₆H₃ 2,5-diBr-3-thienyl 2,3,4-triCl-1H-pyrrol-1-yl 51 2-Br-5-Me-C₆H₃ 2-F-5-Cl-3-thienyl 2,3,5-triCl-1H-pyrrol-1-yl 52 3-Br-6-Me-C₆H₃ 2-Cl-5-F-3-thienyl 2,3-diCl-4-Me-1H-pyrrol-1-yl 53 2-CN-3-F-C₆H₃ 2-F-5-Br-3-thienyl 2,3-diCl-5-Me-1H-pyrrol-l-yl 54 2-CN-5-F-C₆H₃ 2-Br-5-F-3-thienyl 2,4-diCl-3-Me-1H-pyrrol-1-yl 55 2-CN-6-F-C₆H₃ 2-Cl-5-Br-3-thienyl 2,4-diCl-5-Me-1H-pyrrol-1-yl 56 2-CN-3-Cl-C₆H₃ 2-Br-5-Cl-3-thienyl 2,5-diCl-3-Me-1H-pyrrol-l-yl 57 2-CN-5-Cl-C₆H₃ 2-n-Pr-5-F-3-thienyl 2-CN-3,5-diMe-1H-pyrrol-1-yl 58 2-CN-6-CL-C₆H₃ 2-CN-5-F-3-thienyl 2-CN-4,5-diMe-1H-pyrrol-1-yl 59 2-CN-5-Br-C₆H₃ 2-CN-5-Cl-3-thienyl 2-CN-3,4-diCl-1H-pyrrol-1-yl 60 2-CN-3-CF₃-C₆H₃ 2-CN-5-Br-3-thienyl 2-CN-3,5-diCl-1H-pyrrol-1-yl 61 2-CN-3-Me-C₆H₃ 2-CN-5-Me-3-thienyl 2-CN-4,5-diCl-1H-pyrrol-l-yl 62 2-CN-5-Me-C₆H₃ 1H-pyrrol-1-yl 2-CN-3-Cl-4-Me-1H-pyrrol-1-yl 63 2-CN-6-Me-C₆H₃ 2-F-1H-pyrrol-1-yl 2-CN-3-Cl-5-Me-1H-pyrrol-l-yl 64 2-Br-4-F-C₆H₃ 3-F-1H-pyrrol-1-yl 2-CN-3-Me-4-Cl-1H-pyrrol-1-yl 65 2-Br-5-F-C₆H₃ 2-I-1H-pyrrol-1-yl 2-CN-3-Me-5-Cl-1H-pyrrol-1-yl 66 2-Cl-3-Me-C₆H₃ 2-Cl-1H-pyrrol-1-yl 2-CN-4-Me-5-Cl-1H-pyrrol-1-yl 67 2-Cl-5-Me-C₆H₃ 3-Cl-1H-pyrrol-1-yl 2-CN-4-Cl-5-Me-1H-pyrrol-1-yl 68 2-Cl-6-Me-C₆H₃ 2-CN-1H-pyrrol-1-yl 2-CN-4-Br-5-Me-1H-pyrrol-1-yl 69 3-Cl-5-Me-C₆H₃ 2-Br-1H-pyrrol-1-yl 9 3 4, 5-tetraCl-1H-pyrrol-1-yl 70 2-n-Pr-3-F-C₆H₃ 2-n-Pr-1H-pyrrol-1-yl 2,3,5-triCl-4-Me-1H-py-rol-1-yl 71 2-n-Pr-4-F-C₆H₃ 2-i-Pr-1H-pyrrol-1-yl 2,5-diCl-3,4-diMe-1H-pyrrol-1-yl 72 2-n-Pr-5-F-C₆H₃ 2-n-Bu-1H-pyrrol-1-yl 2,3,4-triCl-5-CN-1H-pyrrol-1-yl 73 2-n-Pr-3-Cl-C₆H₃ 2-CH₂CN-1H-pyrrol-1-yl 2,3,4-triMe-5-CN-1H-pyrrol-1-yl 74 2-n-Pr-5-Cl-C₆H₃ 2-t-Bu-1H-pyrrol-1-yl 2,3-Cl-4-Me-5-CN-1H-pyrrol-1-yl 75 2-n-Pr-5-Br-C₆H₃ 5-Et-1H-pyrrol-1-yl 2,4-Cl-3-Me-5-CN-1H-pyrrol-1-yl 76 2-n-Pr-5-Me-C₆H₃ 2-(C≡CH)-1H-pyrrol-1-yl 3,4-Cl-2-Me-5-CN-1H-pyrrol-1-yl

TABLE 2

Z = Column 1 Column 2 Column 3 1 C₆H₅ 2-CN-5-I-C₆H₃ 3-CH₂Cl-2-thienyl 2 2-F-C₆H₄ 2-CN-6-Me-C₆H₃ 3-CH₂Br-2-thienyl 3 3-F-C₆H₄ 2-Br-4-F-C₆H₃ 3-(CH₂CN)-2-thienyl 4 4-F-C₆H₄ 2-Br-5-F-C₆H₃ 5-SiMe₃-2-thienyl 5 2-Cl-C₆H₄ 3-Br-6-F-C₆H₃ 3-(CH═CH₂)-2-thienyl 6 3-Cl-C₆H₄ 2-Cl-3-Me-C₆H₃ 3-(CH═CHMe)-2-thienyl 7 4-Cl-C₆H₄ 2-Cl-5-Me-C₆H₃ 3-(CH₂CH═CH₂)-2-thienyl 8 2-Br-C₆H₄ 2-Cl-6-Me-C₆H₃ 3-(CH₂C═CH)-2-thienyl 9 3-Br-C₆H₄ 3-Cl-5-Me-C₆H₃ 3-(C≡CMe)-2-thienyl 10 4-Br-C₆H₄ 3-Cl-6-Me-C₆H₃ 3-(CH≡CHCN)-2-thienyl 11 2-I-C₆H₄ 2-n-Pr-3-F-C₆H₃ 3,5-diF-2-thienyl 12 3-I-C₆H₄ 2-n-Pr-5-F-C₆H₃ 3,5-diCl-2-thienyl 13 4-I-C₆H₄ 2-n-Pr-6-F-C₆H₃ 3-F-5-Cl-2-thienyl 14 2-Me-C₆H₄ 2-n-Pr-3-Cl-C₆H₃ 3-Cl-5-F-2-thienyl 15 3-Me-C₆H₄ 2-n-Pr-5-Cl-C₆H₃ 3-F-5-Br-2-thienyl 16 4-Me-C₆H₄ 2-n-Pr-5-Br-C₆H₃ 3-Br-4-F-2-thienyl 17 2-Et-C₆H₄ 2-n-Pr-5-Me-C₆H₃ 3-Br-5-F-2-thienyl 18 3-Et-C₆H₄ 2-n-Pr-6-CN-C₆H₃ 3-F-5-Me-2-thienyl 19 2-CN-C₆H₄ 2-Cl-3-F-C₆H₃ 3-Me-5-F-2-thienyl 20 2-CF₃-C₆H₄ 2-Cl-5-F-C₆H₃ 3-Br-5-Cl-2-thienyl 21 2-n-Pr-C₆H₄ 2-Cl-6-F-C₆H₃ 3-Cl-5-Me-2-thienyl 22 3-n-Pr-C₆H₄ 3-Cl-2-F-C₆H₃ 3-Me-5-Cl-2-thienyl 23 2-i-Pr-C₆H₄ 3-Cl-6-F-C₆H₃ 3-Br-5-Me-2-thienyl 24 3-i-Pr-C₆H₄ 4-Cl-2-F-C₆H₃ 3-Me-5-Br-2-thienyl 25 3-SCF₃-C₆H₄ 2-F-3-Me-C₆H₃ 3-n-Pr-5-Cl-2-thienyl 26 2-n-Bu-C₆H₄ 2-F-5-Me-C₆H₃ 3-CN-5-F-2-thienyl 27 3-SiMe₃-C₆H₄ 2-P-6-Me-C₆H₃ 3-CN-5-Cl-2-thienyl 28 3-SCF₂H-C₆H₄ 3-F-6-Me-C₆H₃ 3-CN-5-Br-2-thienyl 29 2-CH₂F-C₆H₄ 2,3,4-triF-C₆H₂ 3-CN-5-Me-2-thienyl 30 3-CH₂F-C₆H₄ 2,3,5-triF-C₆H₂ 3-thienyl 31 2-CH₂Cl-C₆H₄ 2,3,6-triF-C₆H₂ 2-F-3-thienyl 32 2-CH₂Br-C₆H₄ 2,4,5-triF-C₆H₂ 4-F-3-thienyl 33 2-CH₂CN-C₆H₄ 2,3,5-triCl-C₆H₂ 5-F-3-thienyl 34 2-CH₂CH₂F-C₆H₄ 2,3,6-triCl-C₆H₂ 2-I-3-thienyl 35 2-CH₂CH₂CL-C₆H₄ 2,4,6-triCl-C₆H₂ 5-I-3-thienyl 36 2-CH₂CH₂CN-C₆H₄ 2,5-diF-3-Cl-C₆H₂ 2-Me-3-thienyl 37 2-(CH═CH₂)-C₆H₄ 2,5-diF-6-Cl-C₆H₂ 5-Me-3-thienyl 38 2-(CH═CHMe)-C₆H₄ 2,3-diCl-5-F-C₆H₂ 2-Et-3-thienyl 39 2-(CH₂CH═CH₂)-C₆H₄ 2,3-diCl-6-F-C₆H₂ 2-Cl-3-thienyl 40 2-(CH═CHCN)-C₆H₄ 2,5-diCl-3-F-C₆H₂ 4-Cl-3-thienyl 41 2-(C≡CH)-C₆H₄ 2,5-diCl-6-F-C₆H₂ 5-Cl-3-thienyl 42 2-(CH₂C≡CH)-C₆H₄ 2,6-diCl-3-F-C₆H₂ 2-CN-3-thienyl 43 2-(C≡CMe)-C₆H₄ 2,3-diF-5-Me-C₆H₂ 2-(C≡CH)-3-thienyl 44 2-(t-Bu)-C₆H₄ 2,5-diF-3-Me-C₆H₂ 2-Br-3-thienyl 45 2-(CH₂C≡CMe)-C₆H₄ 2,5-diF-6-Me-C₆H₂ 5-Br-3-thienyl 46 2-[CH(F)Me]-C₆H₄ 2-CN-3,5-diF-C₆H₂ 2-n-Pr-3-thienyl 47 2-[CH(Cl)Me]-C₆H₄ 2-CN-3,6-diF-C₆H₂ 2-i-Pr-3-thienyl 48 2-[CH(Br)Me]-C₆H₄ 2-CN-5,6-diF-C₆H₂ 2-n-Bu-3-thienyl 49 2-[CH(CN)Me]-C₆H₄ 2-CN-3-F-5-Cl-C₆H₂ 2-CH₂F-3-thieny- 50 2-[CH(CN)CH₂Me]-C₆H₄ 2-CN-3-Me-5-Cl-C₆H₂ 2-(CH₂CN)-3-thienyl 51 2-(CH₂CH₂C≡CH)-C₆H₄ 2-CN-3-Me-5-F-C₆H₂ 2-t-Bu-3-thienyl 52 2,3-diF-C₆H₃ 2-CN-5-F-6-Cl-C₆H₂ 2-(CH₂CH₂CN)-3-thienyl 53 2,4-diF-C₆H₃ 2-Cl-3-F-5-Me-C₆H₂ 2-(CHCH₂)-3-thienyl 54 2 ,5-diF-C₆H₃ 2-F-3-Cl-5-Me-C₆H₂ 2-(CH═CHMe)-3-thienyl 55 2,6-diF-C₆H₃ 2,3,4,5-tetraF-C₆H 2-(CH₂CH≡CH₂)-3-thienyl 56 3,4-diF-C₆H₃ 2,3,4,6-tetraF-C₆H 2-(CH₂C≡CH)-3-thienyl 57 3,5-diF-C₆H₃ 2,3,5,6-tetraF-C₆H 2-(C≡CMe)-3-thienyl 58 2,5-diCl-C₆H₃ 2-thienyl 2-(CH≡CHCN)-3-thienyl 59 2,6-diCl-C₆H₃ 3-F-2-thienyl 2,4-diF-3-thienyl 60 3,5-diCl-C₆H₃ 4-F-2-thienyl 2,5-diF-3-thienyl 61 2,5-diBr-C₆H₃ 5-F-2-thienyl 4,5-diF-3-thienyl 62 2-Br-5-Cl-C₆H₃ 5-1-2-thienyl 2,5-diCl-3-thienyl 63 2-Br-5-Me-C₆H₃ 3-Me-2-thienyl 2,5-diBr-3-thienyl 64 2-CN-3-F-C₆H₃ 5-Me-2-thienyl 2-Cl-5-Br-3-thienyl 65 2-CN-4-F-C₆H₃ 3-Cl-2-thienyl 2-Br-5-Cl-3-thienyl 66 2-CN-5-F-C₆H₃ 4-Cl-2-thienyl 2-Br-5-Me-3-thienyl 67 2-CN-6-F-C₆H₃ 5-Cl-2-thienyl 2-Me-5-Br-3-thienyl 68 2-CN-3-Cl-C₆H₃ 3-CN-2-thienyl 2-n-Pr-5-Cl-3-thienyl 69 2-CN-5-Cl-C₆H₃ 5-(C≡CH)-2-thienyl 2-n-Pr-5-Br-3-thienyl 70 2-CN-6-Cl-C₆H₃ 3-Br-2-thienyl 2-CN-5-Cl-3-thienyl 71 2-CN-5-Br-C₆H₃ 5-Br-2-thienyl 2-CN-5-Br-3-thienyl 72 2-CN-3-I-C₆H₃ 3-n-Pr-2-thienyl 2-CN-5-Me-3-thienyl 73 2-CN-3-Me-C₆H₃ 5-n-Pr-2-thienyl 2-CN-5-t-Bu-C₆H₃ 74 2-CN-5-Me-C₆H₃ 5-i-Pr-2-thienyl

TABLE 3

Z = Column 1 Column 2 Column 3 1 C₆H₅ 2-CN-3-Cl-C₆H₃ 2,3,5,6-tetraCl-C₆H 2 2-F-C₆H₄ 2-CN-4-Cl-C₆H₃ 2,3.5-triCl-6-CN-C₆H 3 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ 2,3,4-triF-6-CN-C₆H 4 4-F-C₆H₄ 2-CN-6-Cl-C₆H₃ 2,5-diCl-3,6-diF-C₆H 5 2-Cl-C₆H₄ 2-CN-5-Br-C₆H₃ 2,5-diF-3-Cl-6-CN-C₆H 6 3-Cl-C₆H₄ 2-CN-3-I-C₆H₃ 1H-pyrrol-1-yl 7 4-Cl-C₆H₄ 2-CN-3-CF₃-C₆H₃ 2-F-1H-pyrrol-1-yl 8 2-Br-C₆H₄ 2-CN-6-CF₃-C₆H₃ 3-F-1H-pyrrol-1-yl 9 3-Br-C₆H₄ 2-CN-3-Me-C₆H₃ 2-I-1H-pyrrol-1-yl 10 4-Br-C₆H₄ 2-CN-5-Me-C₆H₃ 2-Cl-1H-pyrrol-1-yl 11 2-I-C₆H₄ 2-Br-4-F-C₆H₃ 3-Cl-1H-pyrrol-1-yl 12 3-I-C₆H₄ 2-Br-5-F-C₆H₃ 2-CN-1H-pyrrol-1-yl 13 4-I-C₆H₄ 3-Br-6-F-C₆H₃ 2-Br-1H-pyrrol-1-yl 14 2-Me-C₆H₄ 2-Cl-3-Me-C₆H₃ 2-n-Pr-1H-pyrrol-1-yl 15 3-Me-C₆H₄ 2-Cl-5-Me-C₆H₃ 2-n-Bu-1H-pyrrol-1-yl 16 4-Me-C₆H₄ 3-Cl-5-Me-C₆H₃ 2-t-Bu-1H-pyrrol-1-yl 17 2-Et-C₆H₄ 2-n-Pr-3-F-C₆H₃ 2,3-diCl-1H-pyrrol-1-yl 18 3-Et-C₆H₄ 2-n-Pr-4-F-C₆H₃ 2,4-diCl-1H-pyrrol-1-yl 19 2-CN-C₆H₄ 2-n-Pr-5-F-C₆H₃ 2,5-diCl-1H-pyrrol-1-yl 20 2-CF₃-C₆H₄ 2-n-Pr-6-F-C₆H₃ 2,3-diBr-1H-pyrrol-1-yl 21 2-n-Pr-C₆H₄ 2-n-Pr-3-Cl-C₆H₃ 2,4-diBr-1H-pyrrol-1-yl 22 3-n-Pr-C₆H₄ 2-n-Pr-5-Cl-C₆H₃ 2,5-diBr-1H-pyrrol-1-yl 23 2-i-Pr-C₆H₄ 2-n-Pr-5-Br-C₆H₃ 2-Cl-3-Br-1H-pyrrol-1-yl 24 3-i-Pr-C₆H₄ 2-n-Pr-5-Me-C₆H₃ 2-Cl-4-Br-1H-pyrrol-1-yl 25 2-n-Bu-C₆H₄ 2-Cl-3-F-C₆H₃ 2-Cl-5-Br-1H-pyrrol-1-yl 26 3-SiMe₃-C₆H₄ 2-Cl-4-F-C₆H₃ 3-Cl-5-Br-1H-pyrrol-1-yl 27 2-CH₂F-C₆H₄ 2-Cl-5-F-C₆H₃ 4-Cl-5-Br-1H-pyrrol-1-yl 28 3-CH₂F-C₆H₄ 2-Cl-6-F-C₆H₃ 2-Cl-3-Me-1H-pyrrol-1-yl 29 2-CH₂Cl-C₆H₄ 3-Cl-2-F-C₆H₃ 2-Cl-4-Me-1H-pyrrol-1-yl 30 2-CH₂Br-C₆H₄ 3-Cl-6-F-C₆H₃ 2-Cl-5-Me-1H-pyrrol-1-yl 31 2-CH₂CN-C₆H₄ 2-F-3-Me-C₆H₃ 2-Br-3-Me-1H-pyrrol-1-yl 32 2-CH₂CH₂F-C₆H₄ 2-F-5-Me-C₆H₃ 2-Br-4-Me-1H-pyrrol-1-yl 33 2-CH₂CH₂Cl-C₆H₄ 2-F-6-Me-C₆H₃ 2-Br-5-Me-1H-pyrrol-1-yl 34 2-CH₂CH₂CN-C₆H₄ 3-F-6-Me-C₆H₃ 3-Br-4-Me-1H-pyrrol-1-yl 35 2-(CH═CH₂)-C₆H₄ 2,3,4-triF-C₆H₂ 2-CN-3-Cl-1H-pyrrol-1-yl 36 2-(CH═CHMe)-C₆H₄ 2,3,5-triF-C₆H₂ 2-CN-4-Cl-1H-pyrrol-1-yl 37 2-(CH₂CH═CH₂)-C₆H₄ 2,3,6-triF-C₆H₄ 2-CN-5-Cl-1H-pyrrol-1-yl 38 2-(C≡CH)-C₆H₄ 2,4,5-triF-C₆H₂ 2-CN-3-Br-1H-pyrrol-1-yl 39 2-(CH₂C≡CH)-C₆H₄ 2,4,6-triF-C₆H₂ 2-CN-4-Br-1H-pyrrol-1-yl 40 2-(C≡CMe)-C₆H₄ 2,3,5-triCl-C₆H₂ 2-CN-5-Br-1H-pyrrol-1-yl 41 2-(C≡CCH₂Me)-C₆H₄ 2,3,6-triCl-C₆H₂ 2-CN-3-Me-1H-pyrrol-1-yl 42 2-(t-Bu)-C₆H₄ 2,3-diF-5-Cl-C₆H₂ 2-CN-4-Me-1H-pyrrol-1-yl 43 2-[CH(F)Me]-C₆H₄ 2,3-diF-6-Cl-C₆H₂ 2-CN-5-Me-1H-pyrrol-1-yl 44 2-[CH(Cl)Me]-C₆H₄ 2,5-diF-3-Cl-C₆H₂ 2-CN-5-n-Pr-1H-pyrrol-1-yl 45 2-[CH(Br)Me]-C₆H₄ 2,5-diF-6-Cl-C₆H₂ 2,3,4-triCl-1H-p-rol-1-yl 46 2-[CH(CN)Me]-C₆H₄ 2,6-diF-3-Cl-C₆H₂ 2,3,5-triCl-1H-pyrrol-1-yl 47 2-[CH═C(Me)₂]-C₆H₄ 2,3-diCl-5-F-C₆H₂ 2,3-diCl-4-Me-1H-pyrrol-1-yl 48 2-[CH(Me)CH═CH₂]-C₆H₄ 2,5-diCl-3-F-C₆H₂ 2,3-diCl-5-Me-1H-pyrrol-1-yl 49 2-(CH₂C(Me)═CH₂)-C₆H₄ 2,5-diCl-6-F-C₆H₂ 2,4-diCl-3-Me-1H-pyrrol-1-yl 50 2-(CH₂CH₂C-CH)-C₆H₄ 2,3-diF-5-Me-C₆H₂ 2,4-diCl-5-Me-1H-pyrrol-1-yl 51 2,3-diF-C₆H₃ 2,5-diF-3-Me-C₆H₂ 2,5-diCl-3-Me-1H-pyrrol-1-yl 52 2,4-diF-C₆H₃ 2,5-diF-6-Me-C₆H₂ 2-CN-3,5-diMe-1H-pyrrol-1-yl 53 2,5-diF-C₆H₃ 2,5-diCl-3-Me-C₆H₂ 2-CN-4,5-diMe-1H-pyrrol-1-yl 54 2,6-diF-C₆H₃ 2,5-diCl-6-Me-C₆H₂ 2-CN-3,5-diCl-1H-pyrrol-1-yl 55 3,4-diF-C₆H₃ 2-CN-3,5-diMe-C₆H₂ 2-CN-4,5-diCl-1H-pyrrol-1-yl 56 3,5-diF-C₆H₃ 2-CN-3,5-diCl-C₆H₂ 2-CN-3-Cl-4-Me-1H-pyrrol-1-yl 57 2,3-diCl-C₆H₃ 2-CN-3,5-diF-C₆H₂ 2-CN-3-Cl-5-Me-1H-pyrrol-1-yl 58 2,4-diCl-C₆H₃ 2-CN-5,6-diF-C₆H₂ 2-CN-3-Me-4-Cl-1H-pyrrol-1-yl 59 2,5-diCl-C₆H₃ 2-CN-3-F-5-Cl-C₆H₂ 2-CN-3-Me-5-Cl-1H-pyrrol-1-yl 60 2,6-diCl-C₆H₃ 2-CN-3-Me-5-Cl-C₆H₂ 2-CN-4-Me-5-Cl-1H-pyrrol-1-yl 61 3,4-diCl-C₆H₃ 2-CN-3-Me-5-F-C₆H₂ 2-CN-4-Cl-5-Me-1H-pyrrol-1-yl 62 3,5-diCl-C₆H₃ 2-CN-5-F-6-Cl-C₆H₂ 2-CN-4-Br-5-Me-1H 63 2,5-diBr-C₆H₃ 2-Cl-3-F-5-Me-C₆H₂ 2,3,4,5-tetraCl-1H-pyrrol-1-yl 64 2-Br-5-Cl-C₆H₃ 2-Cl-3-F-6-Me-C₆H₂ 2,3,5-triCl-4-Me-1H-pyrrol-1-yl 65 3-Br-6-Cl-C₆H₃ 2-F-3-Cl-5-Me-C₆H₂ 2,5-diCl-3,4-diMe-1H-pyrrol-1-yl 66 2-Br-5-Me-C₆H₃ 2,3,4,5-tetraF-C₆H 2,3,4-triCl-5-CN-1H-pyrrol-1-yl 67 3-Br-6-Me-C₆H₃ 2,3,4,6-tetraF-C₆H 2,3,4-triMe-5-CN-1H-pyrrol-1-yl 68 2-CN-3-F-C₆H₃ 2,3,5,6-tetraF-C₆H 2,3-Cl-4-Me-5-CN-1H-pyrrol-1-yl 69 2-CN-4-F-C₆H₃ 2,3,4,5-tetraCl-C₆H 2,4-Cl-3-Me-5-CN-1H-pyrrol-1-yl 70 2-CN-5-F-C₆H₃ 2,3,4,6-tetraCl-C₆H 3,4-Cl-2-Me-5-CN-1H-pyrrol-1-yl 71 2-CN-6-F-C₆H₃

TABLE 4

Z = R1 R2 R⁶ X Column 1 Column 2 H H t-Bu O C₆H₅ 2,5-diF-C₆H₃ H H t-Bu O 2-F-C₆H₄ 2,5-diCl-C₆H₃ H H t-Bu O 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ H H t-Bu O 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ H H t-Bu O 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ H H t-Bu O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ H H t-Bu CH₂ C₆H₅ 2,5-diF-C₆H₃ H H t-Bu CH₂ 2-F-C₆H₄ 2,5-diCl-C₆H₃ H H t-Bu CH₂ 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ H H t-Bu CH₂ 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ H H t-Bu CH₂ 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ H H t-Bu CH₂ 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ H H t-Bu ═CH C₆H₅ 2,5-diF-C₆H₃ H H t-Bu ═CH 2-F-C₆H₄ 2,5-diCl-C₆H₃ H H t-Bu ═CH 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ H H t-Bu ═CH 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ H H t-Bu ═CH 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ H H t-Bu ═CH 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me Me t-Bu O C₆H₅ 2,5-diF-C₆H₃ Me Me t-Bu O 2-F-C₆H₄ 2,5diCl-C₆H₃ Me Me t-Bu O 2-Cl-C₆H₄ 2-P-5-Cl-C₆H₃ Me Me t-Bu O 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ Me Me t-Bu O 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me Me t-Bu O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me Et t-Bu O C₆H₅ 2,5-diF-C₆H₃ Me Et t-Bu O 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me Et t-Bu O 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ Me Et t-Bu O 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ Me Et t-Bu O 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me Et t-Bu O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H t-Bu CH(Me) C₆H₅ 2,5-diF-C₆H₃ Me H t-Bu CH(Me) 2-F-C₆H₄ 2, 5-diC 1-C₆H₃ Me H t-Bu CH(Me) 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ Me H t-Bu CH(Me) 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ Me H t-Bu CH(Me) 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H t-Bu CH(Me) 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H t-Bu CH(Et) C₆H₅ 2,5-diF-C₆H₃ Me H t-Bu CH(Et) 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H t-Bu CH(Et) 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ Me H t-Bu CH(Et) 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ Me H t-Bu CH(Et) 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H t-Bu CH(Et) 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H t-Bu CH(n-Pr) C₆H₅ 2,5-diF-C₆H₃ Me H t-Bu CH(n-Pr) 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H t-Bu CH(n-Pr) 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ Me H t-Bu CH(n-Pr) 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ Me H t-Bu CH(n-Pr) 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H t-Bu CH(n-Pr) 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H t-Bu ═C(Me) C₆H₅ 2,5-diF-C₆H₃ Me H t-Bu ═C(Me) 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H t-Bu ═C(Me) 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ Me H t-Bu ═C(Me) 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ Me H t-Bu ═C(Me) 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H t-Bu ═C(Me) 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H t-Bu ═C(Et) C₆H₅ 2,5-diF-C₆H₃ Me H t-Bu ═C(Et) 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H t-Bu ═C(Et) 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ Me H t-Bu ═C(Et) 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ Me H t-Bu ═C(Et) 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H t-Bu ═C(Et) 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ H H t-Bu CH₂ 2-thienyl 3,5-diF-2-thienyl H H t-Bu CH₂ 3-F-2-thienyl 3,5-diCl-2-thienyl H H t-Bu CH₂ 3-Cl-2-thienyl 3-Cl-5-F-2-thienyl H H t-Bu CH₂ 3-CN-2-thienyl 3-F-5-Cl-2-thienyl H H t-Bu CH₂ 5-F-2-thienyl 3-CN-5-F-2-thienyl H H t-Bu CH₂ 5-Cl-2-thienyl 3-CN-5-Cl-2-thienyl H H t-Bu ═CH 2-thienyl 3,5-diF-2-thienyl H H t-Bu ═CH 3-F-2-thienyl 3,5-diCl-2-thienyl H H t-Bu ═CH 3-Cl-2-thienyl 3-Cl-5-F-2-thienyl H H t-Bu ═CH 3-CN-2-thienyl 3-F-5-Cl-2-thienyl H H t-Bu ═CH 5-F-2-thienyl 3-CN-5-F-2-thienyl H H t-Bu ═CH 5-Cl-2-thienyl 3-CN-5-Cl-2-thienyl H H t-Bu CH₂ 3-thienyl 2,5-diF-3-thienyl H H t-Bu CH₂ 2-F-3-thienyl 2,5-diCl-3-thienyl H H t-Bu CH₂ 2-Cl-3-thienyl 2-Cl-5-F-3-thienyl H H t-Bu CH₂ 2-CN-3-thienyl 2-F-5-Cl-3-thienyl H H t-Bu CH₂ 5-F-3-thienyl 2-CN-5-F-3-thienyl H H t-Bu CH₂ 5-Cl-3-thienyl 2-CN-5-Cl-3-thienyl H H t-Bu ═CH 3-thienyl 2,5-diF-3-thienyl H H t-Bu ═CH 2-F-3-thienyl 2,5-diCl-3-thienyl H H t-Bu ═CH 2-Cl-3-thienyl 2-Cl-5-F-3-thienyl H H t-Bu ═CH 2-CN-3-thienyl 2-F-5-Cl-3-thienyl H H t-Bu ═CH 5-F-3-thienyl 2-CN-5-F-3-thienyl H H t-Bu ═CH 5-Cl-3-thienyl 2-CN-5-Cl-3-thienyl H H t-Bu CH₂ 1H-pyrrol-1-yl 2,5-diP-1H-pyrrol-1-yl H H t-Bu CH₂ 2-F-1H-pyrrol-1-yl 2,5-diCl-1H-pyrrol-1-yl H H t-Bu CH₂ 2-Cl-1H-pyrrol-1-yl 2-Cl-5-F-1H-pyrrol-1-yl H H t-Bu CH₂ 2-CN-1H-pyrrol-1-yl 2-F-5-Cl-1H-pyrrol-1-yl H H t-Bu CH₂ 5-F-1H-pyrrol-1-yl 2-CN-5-Cl-1H-pyrrol-1-yl H H t-Bu CH₂ 5-Cl-1H-pyrrol-1-yl 2-CN-5-F-1H-pyrrol-1-yl H H t-Bu ═CH 1H-pyrrol-1-yl 2,5-diP-1H-pyrrol-1-yl H H i-Bu ═CH 2-F-1H-pyrrol-1-yl 2-5-diCl-1H-pyrrol-1-yl H H t-Bu ═CH 2,Cl-1H-pyrrol-1-yl 2-Cl-5-F-1H-pyrrol-1yl H H t-Bu ═CH 2-CN-1H-pyrrol-1-yl 2-F-5-Cl-1H-pyrrol-1-yl H H t-Bu ═CH 5-F-1H-pyrrol-1-yl 2-CN-5-Cl-1H-pyrrol-1-yl H H t-Bu ═CH 5-Cl-1H-pyrrol-1-yl 2-CN-5-F-1H-pyrrol-1-yl H H t-Bu O 1H-pyrrol-1-yl 2,5-diF-1H-pyrrol-1-yl H H t-Bu O 2-F-1H-pyrrol-1-yl 2,5-diCl-1H-pyrrol-1-yl H H t-Bu O Z2-Cl-1H-pyrrol-1-yl 2-Cl-5-F-1H-pyrrol-1-yl H H t-Bu O 2-CN-1H-pyrrol-1-yl 2-F-5-Cl-1H-pyrrol-1-yl H H t-Bu O Z5-F-1H-pyrrol-1-yl 2-CN-5-Cl-1H-pyrrol-1-yl H H t-Bu O 5-Cl-1H-pyrrol-1-yl 2-CN-5-F-1H-pyrrol-1-yl Me H CH(Me)C(Me)₃ O C₆H₅ 2,5-diF-C₆H₃ Me H CH(Me)C(Me)₃ O 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H CH(Me)C(Me)₃ O 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ Me H CH(Me)C(Me)₃ O 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ Me H CH(Me)C(Me)₃ O 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H CH(Me)C(Me)₃ O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H CH(Me)C(Me)₃ ═CH C₆H₅ 2,5-diF-C₆H₃ Me H CH(Me)C(Me)₃ ═CH 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H CH(Me)C(Me)₃ ═CH 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ Me H CH(Me)C(Me)₃ ═CH 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ Me H CH(Me)C(Me)₃ ═CH 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H CH(Me)C(Me)₃ ═CH 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H CH(Me)C(Me)₃ CH₂ C₆H₅ 2,5-diF-C₆H₃ Me H CH(Me)C(Me)₃ CH₂ 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H CH(Me)C(Me)₃ CH₂ 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ Me H CH(Me)C(Me)₃ CH₂ 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ Me H CH(Me)C(Me)₃ CH₂ 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H CH(Me)C(Me)₃ CH₂ 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ H H CH(Me)C(Me)₃ O C₆H₅ 2,5-diF-C₆H₃ H H CH(Me)C(Me)₃ O 2-F-C₆H₄ 2,5-diCl-C₆H₃ H H CH(Me)C(Me)₃ O 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ H H CH(Me)C(Me)₃ O 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ H H CH(Me)C(Me)₃ O 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ H H CH(Me)C(Me)₃ O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ H H CH(Me)C(Me)₃ ═CH C₆H₅ 2,5-diF-C₆H₃ H H CH(Me)C(Me)₃ ═CH 2-F-C₆H₄ 2,5-diCl-C₆H₃ H H CH(Me)C(Me)₃ ═CH 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ H H CH(Me)C(Me)₃ ═CH 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ H H CH(Me)C(Me)₃ ═CH 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ H H CH(Me)C(Me)₃ ═CH 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ H H CH(Me)C(Me)₃ CH₂ C₆H₅ 2,5-diF-C₆H₃ H H CH(Me)C(Me)₃ CH₂ 2-F-C₆H₄ 2,5-diCl-C₆H₃ H H CH(Me)C(Me)₃ CH₂ 2-Cl-C₆H₄ 2-F-5-Cl-C₆H₃ H H CH(Me)C(Me)₃ CH₂ 2-CN-C₆H₄ 2-Cl-5-F-C₆H₃ H H CH(Me)C(Me)₃ CH₂ 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ H H CH(Me)C(Me)₃ CH₂ 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H CH(Me)C(Me)₃ CH₂ 1H-pyrrol-1-yl 2,5-diF-1H-pyrrol-1-yl Me H CH(Me)C(Me)₃ CH₂ 2-F-1H-pyrrol-1-yl 2,5-diCl-1H-pyrrol-1-yl Me H CH(Me)C(Me)₃ CH₂ 2-Cl-1H-pyrrol-1-yl 2-Cl-5-F-1H-pyrrol-1-yl Me H CH(Me)C(Me)₃ CH₂ 2-CN-1H-pyrrol-1-yl 2-F-5-Cl-1H-pyrrol-1-yl Me H CH(Me)C(Me)₃ CH₂ 5-F-1H-pyrrol-1-yl 2-CN-5-Cl-1H-pyrrol-1-yl Me H CH(Me)C(Me)₃ CH₂ 5-Cl-1H-pyrrol-1-yl 2-CN-5-F-1H-pyrrol-1-yl Me Ph CH₂CH₃ O 2-CN-C₆H₄ 2-CN-5-F-C₆H₃ Me Ph CH₂CH₃ O 2,5-diF-C₆H₃ 2-Cl-5-F-C₆H₃ Me Ph CH(Me)₂ O 2-CN-C₆H₄ 2-CN-5-F-C₆H₃ Me Ph C(Me)₃ O 2-CN-C₆H₄ 2-CN-5-F-C₆H₃ Me Ph CH₂CH═CH₂ O 2-CN-C₆H₄ 2-CN-5-Cl-1H-pyrrol-1-yl Me Ph CH₂CH═CH₂ O 2,5-diF-C₆H₃ 2-CN-5-F-1H-pyrrol-1-yl Me H CH(Me)C(Me)₃ O 1H-pyrrol-1-yl 2-Cl-5-F-C₆H₃ Me H CH(Me)C(Me)₃ O 2-F-1H-pyrrol-1-yl 2,5-diCl-1H-pyrrol-1-yl Me H CH(Me)C(Me)₃ O 2-Cl-1H-pyrrol-1-yl 2-Cl-5-F-1H-pyrrol-1-yl Me H CH(Me)C(Me)₃ O 2-CN-1H-pyrrol-1-yl 2-F-5-Cl-1H-pyrrol-1-yl Me H CH(Me)C(Me)₃ O 5-F-1H-pyrrol-1-yl 2-CN-5-Cl-1H-pyrrol-1-yl Me H CH(Me)C(Me)₃ O 5-Cl-1H-pyrrol-1-yl 2-CN-5-F-1H-pyrrol-1-yl H H CH(Me)C(Me)₃ CH₂ 1H-pyrrol-1-yl 2,5-diF-1H-pyrrol-1-yl H H CH(Me)C(Me)₃ CH₂ 2-F-1H-pyrrol-1-yl 2,5-diCl-1H-pyrrol-1-yl H H CH(Me)C(Me)₃ CH₂ 2-Cl-1H-pyrrol-1-yl 2-Cl-5-F-1H-pyrrol-1-yl H H CH(Me)C(Me)₃ CH₂ 2-CN-1H-pyrrol-1-yl 2-F-5-Cl-1H-pyrrol-1-yl H H CH(Me)C(Me)₃ CH₂ 5-F-1H-pyrrol-1-yl 2-CN-5-Cl-1H-pyrrol-1-yl H H CH(Me)C(Me)₃ CH₂ 5-Cl-1H-pyrrol-1-yl 2-CN-5-F-1H-pyrrol-1-yl Me Ph CH₂CH₃ O 2-F-5-Cl-C₆H₃ 2-CN-5-Cl-C₆H₃ Me Ph CH₂CH₃ O 2-F-5-Me-C₆H₃ 2-CN-5-Me-C₆H₃ Me Ph CH₂CH₂F O 2,5-diF-C₆H₃ 2-CN-5-F-C₆H₃ Me Ph CH₂CH₂Cl O 2,5-diF-C₆H₃ 2-CN-5-F-C₆H₃ Me Ph CH₂C≡CH O 2,5-diF-C₆H₃ 2-CN-5-F-C₆H₃ Me Ph CH₂C(F)═CH₂ O 2,5-diF-C₆H₃ 2-CN-5-F-C₆H₃ H H CH(Me)C(Me)₃ O 1H-pyrrol-1-yl 2,5-diF-1H-pyrrol-1-yl H H CH(Me)C(Me)₃ O 2-F-1H-pyrrol-1-yl 2,5-diCl-1H-pyrrol-1-yl H H CH(Me)C(Me)₃ O 2-Cl-1H-pyrrol-1-yl 2-Cl-5-F-1H-pyrrol-1-yl H H CH(Me)C(Me)₃ O 2-CN-1H-pyrrol-1-yl 2-F-5-Cl-1H-pyrrol-1-yl H H CH(Me)C(Me)₃ O 5-F-1H-pyrrol-1-yl 2-CN-5-Cl-1H-pyrrol-1-yl H H CH(Me)C(Me)₃ O 5-Cl-1H-pyrrol-1-yl 2-CN-5-F-1H-pyrrol-1-yl Me H i-Pr O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H i-Pr O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H i-Pr O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H C(Me)₂CH═CH₂ O 2-OCH₂F-5-F-C₆H₃ 2-F-5-Cl-C₆H₃ Me H C(Me)₂CH═CH₂ O 2-Cl-5-F-C₆H₃ 2-F-5-Br-C₆H₃ Me H C(Me)₂CH═CH₂ O 2-Br-5-F-C₆H₃ 2-F-5-Me-C₆H₃ Me H C(Me)₂CH═CH₂ O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H C(Me)₂CH═CH₂ O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H C(Me)₂CH═CH₂ O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H CH(Me)CH(Me)₂ O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H CH(Me)CH(Me)₂ O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H CH(Me)CH(Me)₂ O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H c-Pr O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H c-Pr O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H c-Pr O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H CH(Me)-c-Pr O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H CH(Me)-c-Pr O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H CH(Me)-c-Pr O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H C(Me)₂CF═CH₂ O 2-OCH₂F-5-F-C₆H₃ 2-F-5-Cl-C₆H₃ Me H C(Me)₂CF═CH₂ O 2-Cl-5-F-C₆H₃ 2-F-5-Br-C₆H₃ Me H C(Me)₂CF═CH₂ O 2-Br-5-F-C₆H₃ 2-F-5-Me-C₆H₃ Me H C(Me)₂CF═CH₂ O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H C(Me)₂CF═CH₂ O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H C(Me)₂CF═CH₂ O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H C(Me)₂CH═CHF O 2-OCH₂F-5-F-C₆H₃ 2F-5-Cl-C₆H₃ Me H G(Me)₂CH═CHF O 2-Cl-5-F-C₆H₃ 2-F-5-Br-C₆H₃ Me H C(Me)₂CH═CHF O 2-Br-5-F-C₆H₃ 2-F-5-Me-C₆H₃ Me H C(Me)₂CH═CHF O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H C(Me)₂CH═CHF O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H C(Me)₂CH═CHF O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H C(Me)(CH₂F)CH═CH₂ O 2-OCH₂F-5-F-C₆H₃ 2-F-5-Cl-C₆H₃ Me H C(Me)(CH₂F)CH═CH₂ O 2-Cl-5-F-C₆H₃ 2-F-5-Br-C₆H₃ Me H C(Me)(CH₂F)CH═CH₂ O 2-Br-5-F-C₆H₃ 2-F-5-Me-C₆H₃ Me H C(Me)(CH₂F)CH═CH₂ O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H C(Me)(CH₂F)CH═CH₂ O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H C(Me)(CH₂F)CH═CH₂ O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H C(Me)(CH₂F)CF═CH₂ O 2-OCH₂F-5-F-C₆H₃ 2-F-5-Cl-C₆H₃ Me H C(Me)(CH₂F)CF═CH₂ O 2-Cl-5-F-C₆H₃ 2-F-5-Br-C₆H₃ Me H C(Me)(CH₂F)CF═CH₂ O 2-Br-5-F-C₆H₃ 2-F-5-Me-C₆H₃ Me H C(Me)(CH₂F)CF═CH₂ O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H C(Me)(CH₂F)CF═CH₂ O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H C(Me)(CH₂F)CF═CH₂ O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H C(CH₂F)₂CH═CH₂ O 2-OCH₂F-5-F-C₆H₃ 2-F-5-Cl-C₆H₃ Me H C(CH₂F)₂CH═CH₂ O 2-Cl-5-F-C₆H₃ 2-F-5-Br-C₆H₃ Me H C(CH₂F)₂CH═CH₂ O 2,-Br-5-F-C₆H₃ 2-F-5-Me-C₆H₃ Me H C(CH₂F)₂CH═CH₂ O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H C(CH₂F)₂CH═CH₂ O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H C(CH₂F)₂CH═CH₂ O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H C(Me)₂CCl═CH₂ O 2-OCH₂F-5-F-C₆H₃ 2-F-5-Cl-C₆H₃ Me H C(Me)₂CCl═CH₂ O 2-Cl-5-F-C₆H₃ 2-F-5-Br-C₆H₃ Me H C(Me)₂CCl═CH₂ O 2-Br-5-F-C₆H₃ 2-F-5-Me-C₆H₃ Me H C(Me)₂CCl═CH₂ O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H C(Me)₂CCl═CH₂ O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H C(Me)₂CCl═CH₂ O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H C(CH₂Cl)₂CH═CH₂ O 2-OCH₂F-5-F-C₆H₃ 2-F-5-Cl-C₆H₃ Me H C(CH₂Cl)₂CH═CH₂ O 2-Cl-5-F-C₆H₃ 2-F-5-Br-C₆H₃ Me H C(CH₂Cl)₂CH═CH₂ O 2-Br-5-F-C₆H₃ 2-F-5-Me-C₆H₃ Me H C(CH₂Cl)₂CH═CH₂ O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H C(CH₂Cl)₂CH═CH₂ O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H C(CH₂Cl)₂CH═CH₂ O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H C(Me)₂-c-Pr O 2-OCH₂F-5-F-C₆H₃ 2-F-5-Cl-C₆H₃ Me H C(Me)₂-c-Pr O 2-Cl-5-F-C₆H₃ 2-F-5-Br-C₆H₃ Me H C(Me)₂-c-Pr O 2-Br-5-F-C₆H₃ 2-F-5-Me-C₆H₃ Me H C(Me)₂-c-Pr O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H C(Me)₂-c-Pr O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H C(Me)₂-c-Pr O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H C(Me)₂CF═CF₂ O 2-OCH₂F-5-F-C₆H₃ 2-F-5-Cl-C₆H₃ Me H C(Me)₂CF═CF₂ O 2-Cl-5-F-C₆H₃ 2-F-5-Br-C₆H₃ Me H C(Me)₂CF═CF₂ O 2-Br-5-P-C₆H₃ 2-F-5-Me-C₆H₃ Me H C(Me)₂CF═CF₂ O 2,5-diF-C₆H₃ 2-Me-5-Cl-C₆H₃ Me H C(Me)₂CF═CF₂ O 2-Cl-5-Me-C₆H₃ 2,5-diCl-C₆H₃ Me H C(Me)₂CF═CF₂ O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H C(CH₃)(C≡CH)CH═CH₂ O 2,5-diF-C₆H₃ 2-F-5-Cl-C₆H₃ Me H C(CH₃)(C≡CH)CH═CH₂ O 2-Cl-5-F-C₆H₃ 2-CN-5-F-C₆H₃ Me H C(CH₃)(C≡CH)CH═CH₂ O 2,5-diCl-C₆H₃ 2-CN-5-Cl-C₆H₃ Me H C(CH═CH₂)₂CH₃ O 2,5-diF-C₆H₃ 2-F-5-Cl-C₆H₃ Me H C(CH═CH₂)₂CH₃ O 2-Cl-5-F-C₆H₃ 2-CN-5-F-C₆H₃ Me H C(CH═CH₂)₂CH₃ O 2,5-diCl-C₆H₃ 2-CN-5-Cl-C₆H₃ Me H C(CH₃)₂CH═CHC≡CH O 2,5-diF-C₆H₃ 2-F-5-Cl-C₆H₃ Me H C(CH₃)₂CH═CHC≡CH O 2-Cl-5-F-C₆H₃ 2-CN-5-F-C₆H₃ Me H C(CH₃)₂CH═CHC≡CH O 2,5-diCl-C₆H₃ 2-CN-5-Cl-C₆H₃

TABLE 5

Z = Column 1 Column 2 Column 3 1 C₆H₅ 2-F-5-Me-C₆H₃ 2-I-1H-pyrrol-1-yl 2 2-F-C₆H₄ 2-F-6-Me-C₆H₃ 2-Cl-1H-pyrrol-1-yl 3 3-F-C₆H₄ 3-F-6-Me-C₆H₃ 3-Cl-1H-pyrrol-1-yl 4 4-F-C₆H₄ 2,3,4-triF-C₆H₂ 2-CN-1H-pyrrol-1-yl 5 2-Cl-C₆H₄ 2,3,5-triF-C₆H₂ 2-Br-1H-pyrrol-1-yl 6 3-Cl-C₆H₄ 2,3,6-triF-C₆H₂ 2-n-Pr-1H-pyrrol-1-yl 7 4-Cl-C₆H₄ 2,3-diF-5-Cl-C₆H₂ 2-1-Pr-1H-pyrrol-1-yl 8 2-Br-C₆H₄ 2,6-diF-3-Cl-C₆H₂ 2-n-Bu-1H-pyrrol-1-yl 9 3-Br-C₆H₄ 2,5-diCl-3-F-C₆H₂ 2-CH₂CN-1H-pyrrol-1-yl 10 4-Br-C₆H₄ 2,5-diCl-6-F-C₆H₂ 2-t-Bu-1H-pyrrol-1-yl 11 2-I-C₆H₄ 2,3-diF-5-Me-C₆H₂ 2-CN-5-F-3-thienyl 12 3-I-C₆H₄ 2,5-diF-3-Me-C₆H₂ 2-Me-4-CN-3-thienyl 13 4-I-C₆H₄ 2,5-diF-6-Me-C₆H₂ 1H-pyrrol-1-yl 14 2-Me-C₆H₄ 2-CN-3,5-diMe-C₆H₂ 2-F-1H-pyrrol-1-yl 15 3-Me-C₆H₄ 2-CN-3,5-diCl-C₆H₂ 5-F-1H-pyrrol-1-yl 16 4-Me-C₆H₄ 2-CN-3,5-diF-C₆H₂ 5-Et-1H-pyrrol-1-yl 17 2-Et-C₆H₄ 2-CN-3,6-diF-C₆H₂ 5-Cl-1H-pyrrol-1-yl 18 2-CN-C₆H₄ 2-CN-S,6-diF-C₆H₂ 2-(C-CH)-1H-pyrrol-1-yl 19 2-CF₃-C₆H₄ 2-CN-3-F-5-Cl-C₆H₂ 5-Br-1H-pyrrol-1-yl 20 2-n-Pr-C₆H₄ 2-CN-3-Me-5-Cl-C₆H₂ 2-n-Pr-1H-pyrrol-1-yl 21 3-n-Pr-C₆H₄ 2-CN-3-Me-5-F-C₆H₂ 2-1-Pr-1H-pyrrol-1-yl 22 2-1-Pr-C₆H₄ 2-Cl-3-F-5-Me-C₆H₂ 2-CF₃-1H-pyrrol-1-yl 23 3-1-Pr-C₆H₄ 2-F-3-Cl-5-Me-C₆H₂ 2,3-diCl-1H-pyrrol-1-yl 24 2-n-Bu-C₆H₄ 2,3,4,5-tetraF-C₆H 2,4-diCl-1H-pyrrol-1-yl 25 2-CH₂F-C₆H₄ 2,3,4,6-tetraF-C₆H 3,4-diCl-1H-pyrrol-1-yl 26 3-CH₂F-C₆H₄ 2,3,5,6-tetraF-C₆H 2,3-diBr-1H-pyrrol-1-yl 27 2-CH₂CN-C₆H₄ 2-thienyl 2,4-diBr-1H-pyrrol-1-yl 28 2-CH₂CH₂F-C₆H₄ 3-F-2-thienyl 4-F-5-Br-1H-p-roI-1-yl 29 2-CH₂CH₂Cl-C₆H₄ 4-F-2-thienyl 2-Cl-3-Br-1H-pyrrol-1-yl 30 2-CH₂CH₂CN-C₆H₄ 5-Et-2-thienyl 2-Cl-4-Br-1H-pyrrol-1-yl 31 2-(CH═CH₂)-C₆H₄ 3-Cl-2-thienyl 3-Cl-4-Br-1H-pyrrol-1-yl 32 2-(C≡CH)-C₆H₄ 4-Cl-2-thienyl 3-Cl-5-Br-1H-pyrrol-1-yl 33 2-(C≡CMe)-C₆H₄ 5-Cl-2-thienyl 4-F-5-Me-1H-pyrrol-1-yl 34 2-(t-Bu)-C₆H₄ 3-(C-CH)-2-thienyl 2-Cl-3-Me-1H-pyrrol-1-yl 35 2-[CH(F)Me]-C₆H₄ 4-Br-2-thienyl 2-Cl-4-Me-1H-pyrrol-1-yl 36 2-[CH(Cl)Me]-C₆H₄ 5-Br-2-thienyl 2-Cl-5-Me-1H-pyrrol-1-yl 37 2-[CH(Br)Me]-C₆H₄ 3-[CH₂CH(CN)Me]-2-thienyl 3-Cl-4-Me-1H-pyrrol-1-yl 38 2-[CH(CN)Me]-C₆H₄ 3-(CH═CH₂)-2-thienyl 3-Cl-5-Me-1H-pyrrol-1-yl 39 2-[CH(CN)CH₂Me]C₆H₄ 3,4-diF-2-thienyl 4-Cl-5-Me-1H-pyrrol-I -yl 40 2,3-diF-C₆H₃ 3,4-diF-2-thienyl 2-Br-3-Me-1H-pyrrol-1-yl 41 2,4-diF-C₆H₃ 3-F-4-Br-2-thienyl 2-Br-4-Me-1H-pyrrol-1-yl 42 2,5-diF-C₆H₃ 3-F-5-Br-2-thienyl 2-Br-5-Me-1H-pyrrol-1-yl 43 2,6-diF-C₆H₃ 3-Br-5-F-2-thienyl 3-Br-4-Me-1H-pyrrol-1-yl 44 3,4-diF-C₆H₃ 4-Br-5-F-2-thienyl 3-Br-5-Me-1H-pyrrol-1-yl 45 3,5-diF-C₆H₃ 3-F-4-Me-2-thienyl 4-Br-5-Me-1H-pyrrol-1-yl 46 2,3-diClC₆H₃ 3-F-5-Me-2-thienyl 2-n-Pr-3-F-1H-pyrrol-1-yl 47 2,4-diCl-C₆H₃ 4-F-5-Me-2-thienyl 2-n-Pr-4-F-1H-pyrrol-1-yl 48 2,5-diCl-C₆H₃ 3-Cl-5-Br-2-thienyl 2-n-Pr-5-F-1H-pyrrol-1-yl 49 2,6-diCl-C₆H₃ 3-Me-4-F-2-thienyl 2-n-Pr-3-Cl-1H-pyrrol-1-yl 50 3,4-diCl-C₆H₃ 3-Me-5-F-2-thienyl 2-n-Pr-4-Cl-1H-pyrrol-1-yl 51 3,5-diCl-C₆H₃ 3-Br-5-Cl-2-thienyl 2-n-Pr-5-Cl-1H-pyrrol-1-yl 52 2, 5-diBr-C₆H₃ 4-Br-5-Cl-2-thienyl 2-n-Pr-3-Br-1H-pyrrol-1-yl 53 2-Br-5-Cl-C₆H₃ 3-Cl-5-Me-2-thienyl 2-n-Pr-4-Br-1H-pyrrol-1-yl 54 2-Br-5-Me-C₆H₃ 3-Me-5-Cl-2-thienyl 2-n-Pr-5-Br-1H-pyrrol-1-yl 55 3-Br-6-Me-C₆H₃ 3-Br-5-Me-2-thienyl 2-CN-3-F-1H-pyrrol-1-yl 56 2-CN-3-F-C₆H₃ 3-Me-5-Br-2-thienyl 2-CN-4-F-1H-pyrrol-1-yl 57 2-CN-4-F-C₆H₃ 4-Me-5-Br-2-thienyl 2-CN-5-F-1H-pyrrol-1-yl 58 2-CN-5-F-C₆H₃ 3-n-Pr-4-F-2-thienyl 2-CN-3-Cl-1H-pyrrol-1-yl 59 2-CN-6-F-C₆H₃ 3-n-Pr-5-F-2-thienyl 2-CN-4-Cl-1H-pyrrol-1-yl 60 2-CN-3-Cl-C₆H₃ 3-CN-5-Cl-2-thienyl 2-CN-5-Cl-1H-pyrrol-1-yl 61 2-CN-5-Cl-C₆H₃ 3-CN-5-Br-2-thienyl 2-CN-3-Br-1H-pyrrol-1-yl 62 2-CN-5-Br-C₆H₃ 3-thienyl 2-CN-4-Br-1H-pyrrol- Nyl 63 2-CN-3-I-C₆H₃ 2-F-3-thienyl 2-CN-5-Br-1H-pyrrol-1-yl 64 2-CN-3-CF₃-C₆H₃ 4-F-3-thienyl 2-CN-3-Me-1H-pyrrol-1-yl 65 2-CN-6-CF₃-C₆H₃ 5-F-3-thienyl 2-CN-4-Me-1H-pyrrol-1-yl 66 2-CN-3-Me-C₆H₃ 2-Cl-3-thienyl 2-CN-5-Me-1H-pyrrol-1-yl 67 2-CN-4-Me-C₆H₃ 4-Cl-3-thienyl 2-CN-5-n-Pr-1H-pyrrol-1-yl 68 2-CN-5-Me-C₆H₃ 5-Cl-3-thienyl 2,3,4-triCl-1H-pyrrol-1-yl 69 2-CN-6-Me-C₆H₃ 2-CN-3-thienyl 2,3,5-triCl-1H-pyrrol-1-yl 70 2-Br-4-F-C₆H₃ 2-Br-3-thienyl 2,3-diCl-4-Me-1H-pyrrol-1-yl 71 2-Br-5-F-C₆H₃ 5-Br-3-thienyl 2,3-diCl-5-Me-1H-pyrrol-1-yl 72 3-Br-6-F-C₆H₃ 2-n-Pr-3-thienyl 2,4-diCl-3-Me-1H-pyrrol-1-yl 73 2-Cl-5-Me-C₆H₃ 2-(CH₂CN)-3-thienyl 2,4-diCl-5-Me-1H-pyrrol-1-yl 74 3-Cl-5-Me-C₆H₃ 2,5-diCl-3-thienyl 2,5-diCl-3-Me-1H-pyrrol-1-yl 75 3-Cl-6-Me-C₆H₃ 2,5-diBr-3-thienyl 2-CN-3,4-diCl-1H-pyrrol-1-yl 76 2-n-Pr-3-F-C₆H₃ 2-F-5-Cl-3-thienyl 2-CN-3,5-diCl-1H-pyrrol-1-yl 77 2-n-Pr-5-F-C₆H₃ 2-Cl-5-F-3-thienyl 2-CN-4,5-diCl-1H-pyrrol-1-yl 78 2-n-Pr-5-Cl-C₆H₃ 2-F-5-Br-3-thienyl 2-CN-3-Cl-4-Me-1H-pyrrol-1-yl 79 2-n-Pr-5-Br-C₆H₃ 2-Br-5-F-3-thienyl 2-CN-3-Cl-5-Me-1H-pyrrol-1-yl 80 2-n-Pr-5-Me-C₆H₃ 2-Cl-5-Br-3-thienyl 2-CN-3-Me-4-Cl-1H-pyrrol-1-yl 81 2-Cl-3-F-C₆H₃ 2-Br-5-Cl-3-thienyl 2-CN-3-Me-5-Cl-1H-pyrrol-1-yl 82 2-Cl-4-F-C₆H₃ 2-n-Pr-5-F-3-thienyl 2-CN-4-Me-5-Cl-1H-pyrrol-1-yl 83 2-Cl-5-F-C₆H₃ 2-CN-5-F-3-thienyl 2-CN-4-Cl-5-Me-1H-pyrrol-1-yl 84 2-Cl-6-F-C₆H₃ 2-CN-5-Cl-3-thienyl 2-CN-4Br-5-Me-1H-pyrrol-1-yl 85 3-Cl-2-F-C₆H₃ 2-CN-5-Br-3-thienyl 2,3,4-triCl-5-CN-1H-pyrrol-1-yl 86 3-Cl-6-F-C₆H₃ 2-CN-5-Me-3-thienyl 2,3-Cl-4-Me-5-CN-1H-pyrrol-1-yl 87 2-Cl-2-F-C₆H₃ 1H-pyrrol-1-yl 2,4-Cl-3-Me-5-CN-1H-pyrrol-1-yl 88 2-F-3-Me-C₆H₃ 2-F-1H-pyrrol-1-yl 3,4-Cl-2-Me-5-CN-1H-pyrrol-1-yl 89 2-F-4-Me-C₆H₃ 3-F-1H-pyrrol-1-yl

TABLE 6

Z = Column 1 Column 2 Column 3 1 1H-pyrrol-1-yl 2-Cl-4-Me-1H-pyrrol-1-yl 2-CN-5-Me-1H-pyrrol-1-yl 2 2-Cl-1H-pyrrol-1-yl 2-Cl-5-Me-1H-pyrrol-1-yl 2-CN-5-n-Pr-1H-pyrrol-1-yl 3 3-Cl-1H-pyrrol-1-yl 2-Br-3-Me-1H-pyrrol-1-yl 2,3,4-triCl-1H-pyrrol-1-yl 4 2-CN-1H-pyrrol-1-yl 2-Br-4-Me-1H-pyrrol-1-yl 2,3,5-triCl-1H-pyrrol-1-yl 5 2-Br-1H-pyrrol-1-yl 2-Br-5-Me-1H-pyrrol-1-yl 2-CN-3,4-diCl-1H-pyrrol-1-yl 6 3-Br-1H-pyrrol-1-yl 2-n-Pr-5-Br-1H-pyrrol-1-yl 2-CN-3,5-diCl-1H-pyrrol-1-yl 7 2-CH₂CN-1H-pyrrol-1-yl 2-CN-3-Cl-1H-pyrrol-1-yl 2-CN-4,5-diCl-1H-pyrrol-1-yl 8 2,3-diCl-1H-pyrrol-1-yl 2-CN-4-Cl-1H-pyrrol-1-yl 2-CN-3-Cl-4-Me-1H-pyrrol-1-yl 9 2,4-diCl-1H-pyrrol-1-yl 2-CN-5-Cl-1H-pyrrol-1-yl 2-CN-3-Cl-5-Me-1H-pyrrol-1-yl 10 2,5-diCl-1H-pyrrol-1-yl 2-CN-3-Br-1H-pyrrol-1-yl 2-CN-3-Me-4-Cl-1H-pyrrol-1-yl 11 3,4-diCl-1H-pyrrol-1-yl 2-CN-4-Br-1H-pyrrol-1-yl 2-CN-3-Me-5-Cl-1H-pyrrol-1-yl 12 2,3-diBr-1H-pyrrol-1-yl 2-CN-5-Br-1H-pyrrol-1-yl 2-CN-4-Me-5-Cl-1H-pyrrol-1-yl 13 2,4-diBr-1H-pyrrol-1-yl 2-CN-4-Me-1H-pyrrol-1-yl 2-CN-4-Cl-5-Me-1H-pyrrol-1-yl 14 2,5-diBr-1H-pyrrol-1-yl 2,3-diCl-4-Me-1H-pyrrol-1-yl 2,3,4,5-tetraCl-1H-pyrrol-1-yl 15 3,4-diBr-1H-pyrrol-1-yl 2,3-diCl-5-Me-1H-pyrrol-1-yl 2,3,4-triCl-5-Me-1H-pyrrol-1-yl 16 2-Cl-3-Br-1H-pyrrol-1-yl 2,4-diCl-3-Me-1H-pyrrol-1-yl 2,3,5-triCl-4-Me-1H-pyrrol-1-yl 17 2-Cl-4-Br-1H-pyrrol-1-yl 2,4-diCl-5-Me-1H-pyrrol-1-yl 2,4-diCl-3,5-diMe-1H-pyrrol-1-yl 18 2-Cl-5-Br-1H-pyrrol-1-yl 2,5-diCl-3-Me-1H-pyrrol-1-yl 2,5-diCl-3,4-diMe-1H-pyrrol-1-yl 19 3-Cl-4-Br-1H-pyrrol-1-yl 3,4-diCl-5-Me-1H-pyrrol-1-yl 3,4-diCl-2,5-diMe-1H-pyrrol-1-yl 20 3-Cl-5-Br-1H-pyrrol-1-yl 2-CN-3,4-diMe-1H-pyrrol-1-yl 2,3,4-triCl-5-CN-1H-pyrrol-1-yl 21 4-Cl-5-Br-1H-pyrrol-1-yl 2-CN-3,5-diMe-1H-pyrrol-1-yl 2,4-Cl-3-Me-5-CN-1H-pyrrol-1-yl 22 2-Cl-3-Me-1H-pyrrol-1-yl 2-CN-4,5-diMe-1H-pyrrol-1-yl

TABLE 7

Z = Column 1 Column 2 Column 3 1 C₆H₅ 2-CN-4-Me-C₆H₃ 5-Br-2-thienyl 2 2-F-C₆H₄ 2-CN-5-Me-C₆H₃ 3-n-Pr-2-thienyl 3 3-F-C₆H₄ 2-CN-6-Me-C₆H₃ 5-n-Pr-2-thienyl 4 4-F-C₆H₄ 2-Br-4-F-C₆H₃ 5-1-Pr-2-thienyl 5 2-Cl-C₆H₄ 2-Br-5-F-C₆H₃ 3-(CH₂CN)-2-thienyl 6 3-Cl-C₆H₄ 3-Br-6-F-C₆H₃ 3-(CH═CH₂)-2-thienyl 7 4-Cl-C₆H₄ 4-Br-2-F-C₆H₃ 3-(CH═CHMe)-2-thienyl 8 2-Br-C₆H₄ 2-Cl-5-Me-C₆H₃ 3-(CH₂CH═CH₂)-2-thienyl 9 3-Br-C₆H₄ 3-Cl-5-Me-C₆H₃ 3-(CH₂C≡CH)-2-thienyl 10 4-Br-C₆H₄ 3-Cl-6-Me-C₆H₃ 3-(C≡CMe)-2-thienyl 11 2-I-C₆H₄ 2-n-Pr-3-F-C₆H₃ 3-(CH═CHBr)-2-thienyl 12 3-I-C₆H₄ 2-n-Pr-4-F-C₆H₃ 3-(CH═CHCN)-2-thienyl 13 4-I-C₆H₄ 2-n-Pr-5-F-C₆H₃ 3,5-diF-2-thienyl 14 2-Me-C₆H₄ 2-n-Pr-6-F-C₆H₃ 3,5-diCl-2-thienyl 15 3-Me-C₆H₄ 2-n-Pr-3-Cl-C₆H₃ 3,5-diBr-2-thienyl 16 4-Me-C₆H₄ 2-n-Pr-5-Cl-C₆H₃ 3-F-5-Cl-2-thienyl 17 2-Et-C₆H₄ 2-n-Pr-5-Br-C₆H₃ 3-Cl-5-F-2-thienyl 18 2-CN-C₆H₄ 2-n-Pr-5-Me-C₆H₃ 3-F-5-Br-2-thienyl 19 2-CF₃-C₆H₄ 2-n-Pr-6-CN-C₆H₃ 3-Br-4-F-2-thienyl 20 2-n-Pr-C₆H₄ 2-Cl-3-F-C₆H₃ 3-Br-5-F-2-thienyl 21 2-i-Pr-C₆H₄ 2-Cl-4-F-C₆H₃ 3-F-5-Me-2-thienyl 22 2-n-Bu-C₆H₄ 2-Cl-5-F-C₆H₃ 3-Me-5-F-2-thienyl 23 3-SiMe₃-C₆H₄ 2-Cl-6-F-C₆H₃ 3-Br-5-Cl-2-thienyl 24 2-CH₂F-C₆H₄ 3-Cl-2-F-C₆H₃ 3-Cl-5-Me-2-thienyl 25 3-CH₂F-C₆H₄ 3-Cl-6-F-C₆H₃ 3-Me-5-Cl-2-thienyl 26 2-CH₂CN-C₆H₄ 4-Cl-2-F-C₆H₃ 3-Br-5-Me-2-thienyl 27 2-CH₂CH₂F-C₆H₄ 2-F-3-Me-C₆H₃ 3-Me-5-Br-2-thienyl 28 2-CH₂CH₂CN-C₆H₄ 2-F-5-Me-C₆H₃ 3-n-Pr-5-Cl-2-thienyl 29 2-(CH═CH₂)-C₆H₄ 2-F-6-Me-C₆H₃ 3-CN-5-F-2-thienyl 30 2-(CH═CHMe)-C₆H₄ 3-F-6-Me-C₆H₃ 3-CN-5-Cl-2-thienyl 31 2-(CH₂CH═CH₂)-C₆H₄ 2,3,4-triF-C₆H₂ 3-CN-5-Br-2-thienyl 32 2-(CH═CHCl)-C₆H₄ 2,35-triF-C₆H₂ 3-CN-5-Me-2-thienyl 33 2-(CH═CHBr)-C₆H₄ 2,3,6-triF-C₆H₂ 3-thienyl 34 2-(CH═CHCN)-C₆H₄ 2,4,5-triF-C₆H₂ 2-F-3-thienyl 35 2-(C≡CH)-C₆H₄ 2,3,5-triCl-C₆H₂ 4-F-3-thienyl 36 2-(CH₂C-CH)-C₆H₄ 2,3-diF-5-Cl-C₆H₂ 5-F-3-thienyl 37 2-(C≡CMe)-C₆H₄ 2,3-diF-6-Cl-C₆H₂ 2-1-3-thienyl 38 2-(t-Bu)-C₆H₄ 2,5-diF-3-Cl-C₆H₂ 5-1-3-thienyl 39 2-(CH₂C≡CMe)-C₆H₄ 2,5-diF-6-Cl-C₆H₂ 2-Me-3-thienyl 40 2-[CH(F)Me]-C₆H₄ 2,6-diF-3-Cl-C₆H₂ 5-Me-3-thienyl 41 2-[CH(Cl)Me]-C₆H₄ 2,3-diCl-5-F-C₆H₂ 2-Et-3-thienyl 42 2-[CH(Br)Me]-C₆H₄ 2,3-diCl-6-F-C₆H₂ 2-Cl-3-thienyl 43 2-[CH(CN)Me]-C₆H₄ 2,5-diCl-3-F-C₆H₂ 4-Cl-3-thienvl 44 2-[CH(CN)CH₂Me]-C₆H₄ 2,5-diCl-6-F-C₆H₂ 5-Cl-3-thienyl 45 2-[CH═C(Me)2]-C₆H₄ 2, 6-diCl-3-F-C₆H₂ 2-CN-3-thienyl 46 2-[CH(Me)CH═CH2]-C₆H₄ 2,3-diF-5-Me-C₆H₂ 2-(C≡CH)-3-thienyl 47 2-(CH₂C(Me)═CH₂)-C₆H₄ 2,5-diF-3-Me-C₆H₂ 2-Br-3-thienyl 48 2-(CH₂CH₂C-CH)-C₆H₄ 2,5-diF-6-Me-C₆H₂ 5-Br-3-thienyl 49 2,3-diF-C₆H₃ 2-CN-3,5-diCl-C₆H₂ 2-n-Pr-3-thienyl 50 2,4-diF-C₆H₃ 2-CN-3,6-diCl-C₆H₂ 2-1-Pr-3-thienyl 51 2,5-diF-C₆H₃ 2-CN-3,5-diF-C₆H₂ 2-n-Bu-3-thienyl 52 2,6-diF-C₆H₃ 2-CN-3,6-diF-C₆H₂ 2-CH₂F-3-thienyl 53 3,4-diF-C₆H₃ 2-CN-5,6-diF-C₆H₂ 2-(CH₂CN)-3-thienyl 54 3,5-diF-C₆H₃ 2-CN-3-F-5-Cl-C₆H₂ 2-t-Bu-3-thienyl 55 2,3-diCl-C₆H₃ 2-CN-3-Me-5-Cl-C₆H₂ 2-SiMe₃-3-thienyl 56 2,5-diCl-C₆H₃ 2-CN-3-Me-5-F-C₆H₂ 2-(CH₂CH₂CN)-3-thienyl 57 2,5-diBr-C₆H₃ 2-Cl-3-F-5-Me-C₆H₂ 2-(CH═CH₂)-3-thienyl 58 2-Br-5-Cl-C₆H₃ 2-F-3-Cl-5-Me-C₆H₂ 2-(CH═CHMe)-3-thienyl 59 3-Br-2-Cl-C₆H₃ 2,3,4,5-tetraF-C₆H 2-(CH₂CH═CH₂)-3-thienyl 60 3-Br-6-Cl-C₆H₃ 2,3,4,6-tetraF-C₆H 2-(CH₂C≡CH)-3-thienyl 61 4-Br-2-Cl-C₆H₃ 2,3,5,6-tetraF-C₆H 2-(C≡CMe)-3-thienyl 62 2-Br-4-Me-C₆H₃ 2-thienyl 2-(CH═CHCN)-3-thienyl 63 2-Br-5-Me-C₆H₃ 3-F-2-thienyl 2,4-diF-3-thienyl 64 3-Br-6-Me-C₆H₃ 4-F-2-thienyl 2,5-diF-3-thienyl 65 2-CN-3-F-C₆H₃ 5-F-2-thienyl 2,4-diCl-3-thienyl 66 2-CN-4-F-C₆H₃ 5-I-2-thienyl 2,5-diCl-3-thienyl 67 2-CN-5-F-C₆H₃ 3-Me-2-thienyl 2, 5-diBr-3-thienyl 68 2-CN-6-F-C₆H₃ 5-Me-2-thienyl 2-Cl-5-Br-3-thienyl 69 2-CN-3-Cl-C₆H₃ 3-Et-2-thienyl 2-Br-5-Cl-3-thienyl 70 2-CN-5-Cl-C₆H₃ 5-Et-2-thienyl 2-Br-5-Me-3-thienyl 71 2-CN-6-Cl-C₆H₃ 3-Cl-2-thienyl 2-Me-5-Br-3-thienyl 72 2-CN-5-Br-C₆H₃ 4-Cl-2-thienyl 2-n-Pr-5-Cl-3-thienyl 73 2-CN-3-I-C₆H₃ 5-Cl-2-thienyl 2-n-Pr-5-Br-3-thienyl 74 2-CN-3-CF₃-C₆H₃ 3-CN-2-thienyl 2-CN-5-Cl-3-thienyl 75 2-CN-6-CF₃-C₆H₃ 5-(C≡CH)-2-thienyl 2-CN-5-Br-3-thienyl 76 2-CN-3-Me-C₆H₃ 3-Br-2-thienyl 2-CN-5-Me-3-thienyl

TABLE 8

Z = Column 1 Column 2 Column 3 1 C₆H₅ 2-CN-3-Cl-C₆H₃ 2,3,5,6-tetraCl-C₆H 2 2-F-C₆H₄ 2-CN-4-Cl-C₆H₃ 2,3,5-triCl-6-CN-C₆H 3 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ 2,3,4-triF-6-CN-C₆H 4 4-F-C₆H₄ 2-CN-6-Cl-C₆H₃ 2,5-diCl-3,6-diF-C₆H 5 2-Cl-C₆H₄ 2-CN-5-Br-C₆H₃ 2,5-diF-3-Cl-6-CN-C₆H 6 3-Cl-C₆H₄ 2-CN-3-I-C₆H₃ 1H-pyrrol-1-yl 7 4-Cl-C₆H₄ 2-CN-3-CF₃-C₆H₃ 2-F-1H-pyrrol-1-yl 8 2-Br-C₆H₄ 2-CN-6-CF₃-C₆H₃ 3-F-1H-pyrrol-1-yl 9 3-Br-C₆H₄ 2-CN-3-Me-C₆H₃ 2-I-1H-pyrrol-1-yl 10 4-Br-C₆H₄ 2-CN-5-Me-C₆H₃ 2-Cl-1H-pyrrol-1-yl 11 2-I-C₆H₄ 2-Br-4-F-C₆H₃ 3-Cl-1H-pyrrol-1-yl 12 3-I-C₆H₄ 2-Br-5-F-C₆H₃ 2-CN-1H-pyrrol-1-yl 13 4-I-C₆H₄ 3-Br-6-F-C₆H₃ 2-Br-1H-pyrrol-1-yl 14 2-Me-C₆H₄ 2-Cl-3-Me-C₆H₃ 2-n-Pr-1H-pyrrol-1-yl 15 3-Me-C₆H₄ 2-Cl-5-Me-C₆H₃ 2-n-Bu-1H-pyrrol-1-yl 16 4-Me-C₆H₄ 3-Cl-5-Me-C₆H₃ 2-Bu-1H-pyrrol-1-yl 17 2-Et-C₆H₄ 2-n-Pr-3-F-C₆H₃ 2,3-diCl-1H-pyrrol-1-yl 18 2-CN-C₆H₄ 2-n-Pr-4-F-C₆H₃ 2,4-diCl-1H-pyrrol-1-yl 19 2-CF₃-C₆H₄ 2-n-Pr-5-F-C₆H₃ 2,5-diCl-1H-pyrrol-1-yl 20 2-n-Pr-C₆H₄ 2-n-Pr-6-F-C₆H₃ 2,3-diBr-1H-pyrrol-1-yl 21 3-n-Pr-C₆H₄ 2-n-Pr-3-Cl-C₆H₃ 2,4-diBr-1H-pyrrol-1-yl 22 2-1-Pr-C₆H₄ 2-n-Pr-5-Cl-C₆H₃ 2,5-diBr-1H-pyrrol-1-yl 23 3-1-Pr-C₆H₄ 2-n-Pr-5-Br-C₆H₃ 2-Cl-3-Br-1H-pyrrol-1-yl 24 2-n-Bu-C₆H₄ 2-n-Pr-5-Me-C₆H₃ 2-Cl-4-Br-1H-pyrrol-1-yl 25 3-SiMe₃-C₆H₄ 2-Cl-3-F-C₆H₃ 2-Cl-5-Br-1H-pyrrol-1-yl 26 2-CH₂F-C₆H₄ 2-Cl-4-F-C₆H₃ 3-Cl-5-Br-1H-pyrrol-1-yl 27 3-CH₂F-C₆H₄ 2-Cl-5-F-C₆H₃ 4-Cl-5-Br-1H-pyrrol-1-yl 28 2-CH₂Cl-C₆H₄ 2-Cl-6-F-C₆H₃ 2-Cl-3-Me-1H-pyrrol-1-yl 29 2-CH₂Br-C₆H₄ 3-Cl-2-F-C₆H₃ 2-Cl-4-Me-1H-pyrrol-1-yl 30 2-CH₂CN-C₆H₄ 3-Cl-6-F-C₆H₃ 2-Cl-5-Me-1H-pyrrol-1-yl 31 2-CH₂CH₂F-C₆H₄ 2-F-3-Me-C₆H₃ 2-Br-3-Me-1H-pyrrol-1-yl 32 2-CH₂CH₂Cl-C₆H₄ 2-F-5-Me-C₆H₃ 2-Br-4-Me-1H-pyrrol-1-yl 33 2-CH₂CH₂CN-C₆H₄ 2-F-6-Me-C₆H₃ 2-Br-5-Me-1H-pyrrol-1-yl 34 2-(CH═CH₂)-C₆H₄ 3-F-6-Me-C₆H₃ 3-Br-4-Me-1H-pyrrol-1-yl 35 2-(CH═CHMe)-C₆H₄ 2,3,4-triF-C₆H₂ 2-CN-3-Cl-1H-pyrrol-1-yl 36 2-(CH₂CH═CH₂)-C₆H₄ 2,3,5-triF-C₆H₂ 2-CN-4-Cl-1H-pyrrol-1-yl 37 2-(C≡CH)-C₆H₄ 2,3,6-triF-C₆H₂ 2-CN-5-Cl-1H-pyrrol-1-yl 38 2-(CH₂C≡CH)-C₆H₄ 2,4,5-triF-C₆H₂ 2-CN-3-Br-1H-pyrrol-1-yl 39 2-(C≡CMe)-C₆H₄ 2,4,6-triF-C₆H₂ 2-CN-4-Br-1H-pyrrol-1-yl 40 2-(C≡CCH₂Me)-C₆H₄ 2,3,5-triCl-C₆H₂ 2-CN-5-Br-1H-pyrrol-1-yl 41 2-(t-Bu)-C₆H₄ 2,3,6-triCl-C₆H₂ 2-CN-3-Me-1H-pyrrol-1-yl 42 2-[CH(F)Me]-C₆H₄ 2,3-diF-5-Cl-C₆H₂ 2-CN-4-Me-1H-pyrrol-1-yl 43 2-[CH(Cl)Me]-C₆H₄ 2,3-diF-6-Cl-C₆H₂ 2-CN-5-Me-1H-pyrrol-1-yl 44 2-[CH(Br)Me]-C₆H₄ 2,5-diF-3-Cl-C₆H₂ 2-CN-5-n-Pr-1H-pyrrol-1-yl 45 2-[CH(CN)Me]-C₆H₄ 2,5-diF-6-Cl-C₆H₂ 2,3,4-triCl-1H-pyrrol-1-yl 46 2-[CH═C(Me)₂]-C₆H₄ 2,6-diF-3-Cl-C₆H₂ 2,3,5-triCl-1H-pyrrol-1-yl 47 2-[CH(Me)CH═CH₂]-C₆H₄ 2,3-diCl-5-F-C₆H₂ 2,3-diCl-4-Me-1H-pyrrol-1-yl 48 2-(CH₂C(Me)═CH₂)-C₆H₄ 2,5-diCl-3-F-C₆H₂ 2,3-diCl-5-Me-1H-pyrroi-1-yl 49 2-(CH₂CH₂C≡CH)-C₆H₄ 2,5-diCl-6-F-C₆H₂ 2,4-diCl-3-Me-1H-pyrrol-1-yl 50 2,3-diF-C₆H₃ 2,6-diCl-3-F-C₆H₂ 2,4-diCl-5-Me-1H-pyrrol-1-yl 51 2,4-diF-C₆H₃ 2,3-diF-5-Me-C₆H₂ 2,5-diCl-3-Me-1H-pyrrol-1-yl 52 2,5-diF-C₆H₃ 2,5-diF-3-Me-C₆H₂ 2-CN-3,5-diMe-1H-pyrrol-1-yl 53 2,6-diF-C₆H₃ 2,5-diF-6-Me-C₆H₂ 2-CN-4,5-diMe-1H-p yrrol-1-yl 54 3,4-diF-C₆H₃ 2,5-diCl-3-Me-C₆H₂ 2-CN-3,5-diCl-1H-pyrrol-1-yl 55 3,5-diF-C₆H₃ 2,5-diCl-6-Me-C₆H₂ 2-CN-4,5-diCl-1H-pyrrol-1-yl 56 2,3-diCl-C₆H₃ 2-CN-3,5-diMe-C₆H₂ 2-CN-3-Cl-4-Me-1H-pyrrol-1-yl 57 2,4-diCl-C₆H₃ 2-CN-3,5-diCl-C₆H₂ 2-CN-3-Cl-5-Me-1H-pyrrol-1-yl 58 2,5-diCl-C₆H₃ 2-CN-3,5-diF-C₆H₂ 2-CN-3-Me-4-Cl-1H-pyrrol-1-yl 59 2,6-diCl-C₆H₃ 2-CN-5,6-diF-C₆H₂ 2-CN-3-Me-5-Cl-1H-pyrrol-1-yl 60 3,4-diCl-C₆H₃ 2-CN-3-F-5-Cl-C₆H₂ 2-CN-4-Me-5-Cl-1H-pyrrol-1-yl 61 3,5-diCl-C₆H₃ 2-CN-3-Me-5-Cl-C₆H₂ 2-CN-4-Cl-5-Me-1H-pyrrol-1-yl 62 2,5-diBr-C₆H₃ 2-CN-3-Me-5-F-C₆H₂ 2-CN-4-Br-5-Me-1H 63 2-Br-5-Cl-C₆H₃ 2-CN-5-F-6-Cl-C₆H₂ 2,3,4,5-tetraCl-1H-pyrrol-1-yl 64 3-Br-2-Cl-C₆H₃ 2-Cl-3-F-5-Me-C₆H₂ 2,3,5-triCl-4-Me-1H-pyrrol-1-yl 65 3-Br-6-Cl-C₆H₃ 2-Cl-3-F-6-Me-C₆H₂ 2,5-diCl-3,4-diMe-1H-pyrrol-1-yl 66 2-Br-5-Me-C₆H₃ 2-F-3-Cl-5-Me-C₆H₂ 2,3,4-triCl-5-CN-1H-pyrrol-1-yl 67 3-Br-6-Me-C₆H₃ 2,3,4,5-tetraF-C₆H 2,3,4-triMe-5-CN-1H-pyrrol-1-yl 68 2-CN-3-F-C₆H₃ 2,3,4,6-tetraF-C₆H 2,3-Cl-4-Me-5-CN-1H-pyrrol-1-yl 69 2-CN-4-F-C₆H₃ 2,3,5,6-tetraF-C₆H 2,4-Cl-3-Me-5-CN-1H-pyrrol-1-yl 70 2-CN-5-F-C₆H₃ 2,3,4,5-tetraCl-C₆H 3,4-Cl-2-Me-5-CN-1H-pyrrol-1-yl 71 2-CN-6-F-C₆H₃ 2,3,4,6-tetraCl-C₆H

TABLE 9

Z = R¹ R² R³ R⁴ R⁵ X Column 1 Column 2 H H Et Me H CH₂ C₆H₅ 2,5-diF-C₆H₃ H H Et Me H CH₂ 2-F-C₆H₄ 2,5-diCl-C₆H₃ H H Et Me H CH₂ 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ H H Et Me H CH₂ 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ H H Et Me H CH₂ 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ H H Et Me H CH₂ 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ H H Et Me H ═CH C₆H₅ 2,5-diF-C₆H₃ H H Et Me H ═CH 2-F-C₆H₄ 2,5-diCl-C₆H₃ H H Et Me H ═CH 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ H H Et Me H ═CH 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ H H Et Me H ═CH 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ H H Et Me H ═CH 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ H H Et Me H O C₆H₅ 2,5-diF-C₆H₃ H H Et Me H O 2-F-C₆H₄ 2,5-diCl-C₆H₃ H H Et Me H O 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ H H Et Me H O 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ H H Et Me H O 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ H H Et Me H O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me Me Et Me H O C₆H₅ 2,5-diF-C₆H₃ Me Me Et Me H O 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me Me Et Me H O 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me Me Et Me H O 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me Me Et Me H O 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me Me Et Me H O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me Et Et Me H O C₆H₅ 2,5-diF-C₆H₃ Me Et Et Me H O 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me Et Et Me H O 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me Et Et Me H O 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me Et Et Me H O 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me Et Et Me H O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H Et Me H CH(Me) C₆H₅ 2,5-diF-C₆H₃ Me H Et Me H CH(Me) 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H Et Me H CH(Me) 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me H Et Me H CH(Me) 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H Et Me H CH(Me) 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H Et Me H CH(Me) 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H Et Me H CH(Et) C₆H₅ 2,5-diF-C₆H₃ Me H Et Me H CH(Et) 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H Et Me H CH(Et) 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me H Et Me H CH(Et) 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H Et Me H CH(Et) 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H Et Me H CH(Et) 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H Et Me H CH(n-Pr) C₆H₅ 2,5-diF-C₆H₃ Me H Et Me H CH(n-Pr) 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H Et Me H CH(n-Pr) 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me H Et Me H CH(n-Pr) 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H Et Me H CH(n-Pr) 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H Et Me H CH(n-Pr) 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H Et Me H ═C(Me) C₆H₅ 2,5-diF-C₆H₃ Me H Et Me H ═C(Me) 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H Et Me H ═C(Me) 2-G-C₆H₄ 2-Cl-5-F-C₆H₃ Me H Et Me H ═C(Me) 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H Et Me H ═C(Me) 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H Et Me H ═C(Me) 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H Et Me H ═C(Et) C₆H₅ 2,5-diF-C₆H₃ Me H Et Me H ═C(Et) 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H Et Me H ═C(Et) 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me H Et Me H ═C(Et) 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H Et Me H ═C(Et) 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H Et Me H ═C(Et) 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H Et Me H CH₂ C₆H₅ 2,5-diF-C₆H₃ Me H Et Me H CH₂ 2,-F-C₆H₄ 2,5-diCl-C₆H₃ Me H Et Me H CH₂ 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me H Et Me H CH₂ 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H Et Me H CH₂ 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H Et Me H CH₂ 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H Et Me H ═CH C₆H₅ 2,5-diF-C₆H₃ Me H Et Me H ═CH 2-F-C₆H₄ 2,5-diCl--C₆H₃ Me H Et Me H ═CH 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me H Et Me H ═CH 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H Et Me H ═CH 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H Et Me H ═CH 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H Et H Me O C₆H₅ 2,5-diF-C₆H₃ Me H Et H Me O 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H Et H Me O 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me H Et H Me O 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H Et H Me O 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H Et H Me O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H Et H Me CH₂ C₆H₅ 2-5-diF-C₆H₃ Me H Et H Me CH₂ 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H Et H Me CH₂ 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me H Et H Me CH₂ 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H Et H Me CH₂ 3-Cl-C₆H₄ 2-CN-5-F-C61-13 Me H Et H Me CH₂ 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H Et H Me ═CH C₆H₅ 2,5-diF-C₆H₃ Me H Et H Me ═CH 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H Et H Me ═CH 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me H Et H Me ═CH 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H Et H Me ═CH 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H Et H Me ═CH 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H —(CH₂)₄— Me O C₆H₅ 2,5-diF-C₆H₃ Me H —(CH₂)₄— Me O 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H —(CH₂)₄— Me O 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me H —(CH₂)₄— Me O 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H —(CH₂)₄— Me O 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H —(CH₂)₄— Me O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H —(CH₂)₃— Me O C₆H₅ 2,5-diF-C₆H₃ Me H —(CH₂)₃— Me O 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H —(CH₂)₃— Me O 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me H —(CH₂)₃— Me O 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H —(CH₂)₃— Me O 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H —(CH₂)₃— Me O 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ Me H —(CH₂)₃— Me CH₂ C₆H₅ 2,5-diF-C₆H₃ Me H —(CH₂)₃— Me CH₂ 2-F-C₆H₄ 2,5-diCl-C₆H₃ Me H —(CH₂)₃— Me CH₂ 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ Me H —(CH₂)₃— Me CH₂ 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ Me H —(CH₂)₃— Me CH₂ 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ Me H —(CH₂)₃— Me CH₂ 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ H H Et Me H CH₂ C₆H₅ 2,5-diF-C₆H₃ H H Et Me H CH₂ 2-F-C₆H₄ 2,5-diCl-C₆H₃ H H Et Me H CH₂ 2-Cl-C₆H₄ 2-Cl-5-F-C₆H₃ H H Et Me H CH₂ 2-CN-C₆H₄ 2-F-5-Cl-C₆H₃ H H Et Me H CH₂ 3-Cl-C₆H₄ 2-CN-5-F-C₆H₃ H H Et Me H CH₂ 3-F-C₆H₄ 2-CN-5-Cl-C₆H₃ H H Et Me H CH₂ 2-thienyl 3,5-diF-2-thienyl H H Et Me H CH₂ 3-F-2-thienyl 3,5-diCl-2-thienyl H H Et Me H CH₂ 3-Cl-2-thienyl 3-C 1-5-F-2-thienyl H H Et Me H CH₂ 3-CN-2-thienyl 3-F-5-Cl-2-thienyl H H Et Me H CH₂ 5-F-2-thienyl 3-CN-5-F-2-thienyl H H Et Me H CH₂ 5-Cl-2-thienyl 3-CN-5-Cl-2-thienyl H H Et Me H CH₂ 3-thienyl 2,5-diF-3-thienyl H H Et Me H CH₂ 2-F-3-thienyl 2,5-diCl-3-thienyl H H Et Me H CH₂ 2-Cl-3-thienyl 2-Cl-5-F-3-thienyl H H Et Me H CH₂ 2-CN-3-thienyl 2-E-5-Cl-3-thienyl H H Et Me H CH₂ 5-F-3-thienyl 2-CN-5-F-3-thienyl H H Et Me H CH₂ 5-Cl-3-thienyl 2-CN-5-Cl-3-thienyl H H Et Me H CH₂ 1H-pyrrol-1-yl 2,5-diF-1H-pyrrol-1-yl H H Et Me H CH₂ 2-F-1H-pyrrol-1-yl 2,5-diCl-1H-pyrrol-1-yl H H Et Me H CH₂ 2-Cl-1H-pyrrol-1-yl 2-Cl-5-F-1H-pyrrol-1-yl H H Et Me H CH₂ 2-CN-1H-pyrrol-1-yl 2-F-5-Cl-1H-pyrrol-1-yl H H Et Me H CH₂ 5-F-1H-pyrrol-1-yl 2-CN-5-Cl-1H-pyrrol-1-yl H H Et Me H CH₂ 5-Cl-1H-pyrrol-1-yl 2-CN-5-F-1H-pyrrol-1-yl H H Et Me H ═CH 2-thienyl 3,5-diF-2-thienyl H H Et Me H ═CH 3-F-2-thienyl 3,5-diCl-2-thienyl H H Et Me H ═CH 3-Cl-2-thienyl 3-Cl-5-F-2-thienyl H H Et Me H ═CH 3-CN-2-thienyl 3-F-5-Cl-2-thienyl H H Et Me H ═CH 5-F-2-thienyl 3-CN-5-F-2-thienyl H H Et Me H ═CH 5-Cl-2-thienyl 3-CN-5-Cl-2-thienyl H H Et Me H ═CH 3-thienyl 2,5-diF-3-thienyl H H Et Me H ═CH 2-F-3-thienyl 2,5-diCl-3-thienyl H H Et Me H ═CH 2-Cl-3-thienyl 2-Cl-5-F-3-thienyl H H Et Me H ═CH 2-CN-3-thienyl 2-F-5-Cl-3-thienyl H H Et Me H ═CH 5-F-3-thienyl 2-CN-5-F-3-thienyl H H Et Me H ═CH 5-Cl-3-thienyl 2-CN-5-Cl-3-thienyl Me Ph H Me H O 2-CN-C₆H₄ 2-CN-5-F-C₆H₃ Me Ph H Me H O 2-CN-5-Cl-C₆H₃ 2-CN-5-Me-C₆H₃ Me Ph H Me H O 2,5-diF-C₆H₃ 2-F-5-Cl-C₆H₃ Me Ph H H Me O 2-CN-C₆H₄ 2-CN-5-F-C₆H₃ Me Ph H H Me O 2-CN-5-Cl-C₆H₃ 2-CN-5-Me-C₆H₃ Me Ph H H Me O 2,5-diF-C₆H₃ 2-F-5-Cl-C₆H₃ H H Et Me H O 1H-pyrrol-1-yl 2,5-diF-1H-pyrrol-1-yl H H Et Me H O 2-F-1H-pyrrol-1-yl 2,5-diCl-1H-pyrrol-1-yl H H Et Me H O 2-Cl-1H-pyrrol-1-yl 2-Cl-5-F-1H-pyrrol-1-yl H H Et Me H O 2-CN-1H-pyrrol-1-yl 2-F-5-Cl-1H-pyrrol-1-yl H H Et Me H O 5-F-1H-pyrrol-1-yl 2-CN-5-Cl-1H-pyrrol-1-yl H H Et Me H O 5-Cl-1H-pyrrol-1-yl 2-CN-5-F-1H-pyrrol-1-yl Me H H Me Et O 3-F-C₆H₄ 2-CN-3-Cl-C₆H₃ Me H H Me Et O 2,5-diF-C₆H₃ Me H (CH₂)₂CN Me H O 3-F-C₆H₄ 2-CN-3-Cl-C₆H₃ Me H (CH₂)₂CN Me H O 2,5-diF-C₆H₃ Me H (CH₂)₂F Me H O 3-F-C₆H₄ 2-CN-3-Cl-C₆H₃ Me H (CH₂)₂F Me H O 2,5-diF-C₆H₃ Me H CH₂CN Me H O 3-F-C₆H₄ 2-CN-3-Cl-C₆H₃ Me H CH₂CN Me H O 2,5-diF-C₆H₃ Me H (CH₂)₂Cl Me H O 3-F-C₆H₄ 2-CN-3-Cl-C₆H₃ Me H (CH₂)₂Cl Me H O 2,5-diF-C₆H₃ Formulation/Utility

Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible (“wettable”) or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.

The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight. Weight Percent Active Ingredient Diluent Surfactant Water-Dispersible and 5-90 0-94 1-15 Water-soluble Granules, Tablets and Powders. Suspensions, Emulsions, 5-50 40-95  0-15 Solutions (including Emulsifiable Concentrates) Dusts 1-25 70-99  0-5  Granules and Pellets 0.01-99     5-99.99 0-15 High Strength Compositions 90-99  0-10 0-2 

Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, N.J. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, N.J., as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofarfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. Pat. No. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701 and U.S. Pat. No. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Example A Wettable Powder Compound 2 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%. Example B Granule Compound 13 10.0% attapulgite granules (low volatile matter, 90.0%. 0.71/0.30 mm; U.S.S. No. 25-50 sieves) Example C Extruded Pellet Compound 80 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%. Example D Emulsifiable Concentrate Compound 2 20.0% blend of oil soluble sulfonates 10.0% and polyoxyethylene ethers isophorone 70.0%.

The compounds of this invention are useful as plant disease control agents. The present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed or seedling to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound. The compounds and compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Septoria tritici, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequalis, Erysiphe graminis, Uncinula necatur, Puccinia recondita, Puccinia graminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerotheca fuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthora inegasperma, Sclerotinia sclerotiorum, Sclerotium rolfsii, Erysiphe polygoni, Pyrenophora teres, Gaeumannomyces graminis, Rynchosporium secalis, Fusarium roseum, Bremia lactucae and other generea and species closely related to these pathogens.

Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of such agricultural protectants with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorfenapyr, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methyl 7-chloro-2,5-dihydro-2-[[N-(methoxycarbonyl)-N-[4-(trifluoromethoxy)phenyl]amino]carbonyl]indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylate (DPX-JW062), monocrotophos, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, rotenone, sulprofos, tebufenozide, tefluthrin, terbufos, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon and triflumuron; fungicides such as azoxystrobin, benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), bromuconazole, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cymoxanil, cyproconazole, cyprodinil (CGA 219417), diclomezine, dicloran, difenoconazole, dimethomorph, dinconazole, diniconazole-M, dodine, edifenphos, epoxiconazole (BAS 480F), famoxadone, fenarimol, fenbuconazole, fenpiclonil, fenpropidin, fenpropimorph, fluazinam, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, maneb, mepronil, metalaxyl, metconazole, S-methyl 7-benzothiazolecarbothioate (CGA 245704), myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl, penconazole, pencycuron, probenazole, prochloraz, propiconazole, pyrifenox, pyroquilon, quinoxyfen, spiroxamine (KWG4168), sulfur, tebuconazole, tetraconazole, thiabendazole, thiophanate-methyl, thiram, triadimefon, triadimenol, tricyclazole, triticonazole, validamycin and vinclozolin; nematocides such as aldoxycarb and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chiorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.

In certain instances, combinations with other fungicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.

Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compounds can also be applied to the seed to protect the seed and seedling.

Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.

The following TESTS demonstrate the control efficacy of compounds of this invention on specific pathogens. The pathogen control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-E for compound descriptions. The following abbreviations are used in the Index Tables which follow: t=tertiary, n=normal, i=iso, F=fluorine, Br=bromine, Cl=chlorine, I=iodine, Me=methyl, Et=ethyl, Pr=propyl, Bu=butyl, CF₃=trifluoromethyl and CN=cyano. The abbreviation “Ex.” stands for “Example” and is followed by a number indicating in which example the compound is prepared. The abbreviation “Config.” stands for “Configuration”. INDEX TABLE A

The compounds listed below are mixtures of diastereoisomers unless indicated otherwise. Cmpd Conf. at Conf. at No. R¹ * R² ** R⁶ X Z mp(° C.)  1a Me R,S H — t-Bu O C₆H₅ 125-133  1b# Me R,S H — t-Bu O C₆H₅ 132-138  1c## Me R,S H — t-Bu O C₆H₅ 111-114  1d# Me R H — t-Bu O C₆H₅ 78-80  1e## Me R H — t-Bu O C₆H₅ 78-80  2a Me R,S H — t-Bu O 2-F-C₆H₄ Oil^(•)  2b# Me R H — t-Bu O 2-F-C₆H₄ Oil^(•)  2c## Me R H — t-Bu O 2-F-C₆H₄ 100-102  3a Me R,S H — t-Bu O 3-F-C₆H₄ Oil^(•)  3b# Me R,S H — t-Bu O 3-F-C₆H₄ 131-133  3c## Me R,S H — t-Bu O 3-F-C₆H₄ 112-115  3d# Me R H — t-Bu O 3-F-C₆H₄ Oil^(•)  3e## Me R H — t-Bu O 3-F-C₆H₄ 96-98  4a# Me R,S H — t-Bu O 4-F-C₆H₄ Oil^(•)  4b## Me R,S H — t-Bu O 4-F-C₆H₄ 85-88  4c Me R H — t-Bu O 4-F-C₆H₄ Oil^(•)  5a Me R,S H — t-Bu O 2-Cl-C₆H₄ Oil^(•)  5b Me R H — t-Bu O 2-Cl-C₆H₄ 104-107  6a# Me R,S H — t-Bu O 3-Cl-C₆H₄ 112-114  6b Me R,S H — t-Bu O 3-Cl-C₆H₄ Oil^(•)  6c## Me R,S H — t-Bu O 3-Cl-C₆H₄ 132-135  6d# Me R H — t-Bu O 3-Cl-C₆H₄ Oil^(•)  6e## Me R H — t-Bu O 3-Cl-C₆H₄ Oil^(•)  7a# Me R,S H — t-Bu O 4-Cl-C₆H₄ Oil^(•)  7b## Me R,S H — t-Bu O 4-Cl-C₆H₄ 107-110  7c# Me R H — t-Bu O 4-Cl-C₆H₄ Oil^(•)  7d## Me R H — t-Bu O 4-Cl-C₆H₄ Oil^(•)  8a Me R,S H — t-Bu O 2-Br-C₆H₄ 123-125  8b# Me R H — t-Bu O 2-Br-C₆H₄ 103-105  8c## Me R H — t-Bu O 2-Br-C₆H₄ 112-114  9a Me R,S H — t-Bu O 3-Br-C₆H₄ Oil^(•)  9b# Me R H — t-Bu O 3-Br-C₆H₄ 106-108  9c## Me R H — t-Bu O 3-Br-C₆H₄ Oil^(•)  10a# Me R,S H — t-Bu O 4-Br-C₆H₄ Oil^(•)  10b## Me R,S H — t-Bu O 4-Br-C₆H₄ Oil^(•)  10c# Me R H — t-Bu O 4-Br-C₆H₄ Oil^(•)  10d## Me R H — t-Bu O 4-Br-C₆H₄ Oil^(•)  11a Me R,S H — t-Bu O 2-I-C₆H₄ 140-142  11b Me R H — t-Bu O 2-I-C₆H₄ 124-126  12a# Me R H — t-Bu O 3-I-C₆H₄ Oil^(•)  12b## Me R H — t-Bu O 3-I-C₆H₄ Oil^(•)  13a Me R,S H — t-Bu O 2-CN-C₆H₄ Oil^(•)  13b# Me R H — t-Bu O 2-CN-G6H4 Oil^(•)  13c## Me R H — t-Bu O 2-CN-C₆H₄ Oil^(•)  14a# Me R H — t-Bu O 2-Cl-4-Me-C₆H₃ Oil^(•)  14b## Me R H — t-Bu O 2-Cl-4-Me-C₆H₃ Oil^(•)  15a# Me R H — t-Bu O 2-Cl-5-Me-C₆H₃ 103-106  15b## Me R H — t-Bu O 2-Cl-5-Me-C₆H₃ 112-115  16 Me R H — t-Bu O 2-(CH₂CN)-C₆H₄ 120-122  17a Me R,S H — t-Bu O 2-CF₃-C₆H₄ 92-94  17b Me R H — t-Bu O 2-CF₃-C₆H₄ 92-94  18a# Me R H — t-Bu O 3-CF₃-C₆H₄ Oil^(•)  18b## Me R H — t-Bu O 3-CF₃-C₆H₄  98-100  19 Me R H — t-Bu O 2-Me-C₆H₄ 104-107  20a Me R,S H — t-Bu O 2-Et-C₆H₄ 94-97 Ex. 6  20b Me R H — t-Bu O 2-Et-C₆H₄ 102-104  21a Me R,S H — t-Bu O 2-n-Pr-C₆H₄ 95-97  21b Me R H — t-Bu O 2-n-Pr-C₆H₄ 78-81  22 Me R H — t-Bu O 2-i-Pr-C₆H₄ 112-114  23 Me R H — t-Bu O 2-e-Bu-C₆H₄ Oil^(•)  24 Me R H — t-Bu O 4-t-Bu-C₆H₄  97-100  25a Me R,S H — t-Bu O 2-(CH₂CH═CH₂)-C₆H₄ Oil^(•)  25b Me R H — t-Bu O 2-(CH₂CH═CH₂)-C₆H₄ 70-72  26a# Me R H — t-Bu O 2,3-diF-C₆H₃ 86-88  26b## Me R H — t-Bu O 2,3-diF-C₆H₃ 120-122  27a# Me R H — t-Bu O 2,4-diF-C₆H₃ Oil^(•)  27b## Me R H — t-Bu O 2,4-diF-C₆H₃ Oil^(•)  28a# Me R H — t-Bu O 2,5-diF-C₆H₃ 104-106  28b## Me R H — t-Bu O 2,5-diF-C₆H₃ Oil^(•)  28c Me R H — t-Bu O 2,5-diF-C₆H₃ 101-103  29a Me R,S H — t-Bu O 2,6-diF-C₆H₃ Oil^(•)  29b Me R H — t-Bu O 2,6-diF-C₆H₃ Oil^(•)  30a# Me R H — t-Bu O 3,4-diF-C₆H₃ Oil^(•)  30b## Me R H — t-Bu O 3,4-diF-C₆H₃ Oil^(•)  31a# Me R H — t-Bu O 2,3-diCl-C₆H₃ 122-124  31b## Me R H — t-Bu O 2,3-diCl-C₆H₃ 104-106  32a# Me R H — t-Bu O 2,4-diCl-C₆H₃ Oil^(•)  32b## Me R H — t-Bu O 2,4-diCl-C₆H₃ Oil^(•)  33a# Me R H — t-Bu O 2,5-diCl-C₆H₃ 103-105  33b## Me R H — t-Bu O 2,5-diCl-C₆H₃ 103-105  33c Me R H — t-Bu O 2,5-diCl-C₆H₃ 110-112  34 Me R H — t-Bu O 2,6-diCl-C₆H₃ 128-130  35a# Me R H — t-Bu O 3,5-diCl-C₆H₃ 135-137  35b## Me R H — t-Bu O 3,5-diCl-C₆H₃ 121-123  36a# Me R H — t-Bu O 2-F-4-Cl-C₆H₃ Oil^(•)  36b## Me R H — t-Bu O 2-F-4-Cl-C₆H₃ Oil^(•)  37a# Me R H — t-Bu O 2-Cl-4-F-C₆H₃ 88-90  37b## Me R H — t-Bu O 2-Cl-4-F-C₆H₃ Oil^(•)  38 Me R,S H — t-Bu O 2-F-4-Br-C₆H₃ Oil^(•)  39 Me R,S H — t-Bu O 2-CN-3-E-C₆H₃ 143-149  40 Me R,S H — t-Bu O 2-CN-4-F-C₆H₃ 110-116  41 Me R H — t-Bu O 2-CN-5-F-C₆H₃ Oil^(•)  42 Me R,S H — t-Bu O 2-CN-3-Cl-C₆H₃ 115-135  43 Me R H — t-Bu O 2-CN-5-Cl-C₆H₃ Oil^(•)  44 Me R H — t-Bu O 2-CN-5-Br-C₆H₃ Oil^(•)  45 Me R,S H — t-Bu O 2-CN-3-I-C₆H₃ 53-73  46 Me R H — t-Bu O 2-CN-5-I-C₆H₃ Oil^(•)  47 Me R,S H — t-Bu O 2-CN-3-CF₃-C₆H₃ 60-90  48 Me R,S H — t-Bu O 2-CF₃-6-CN-C₆H₃ 135-170  49 Me R,S H — t-Bu O 2-Me-3-Cl-5-CN-1H-pyrrol-1-yl 127-129  50 Me R,S H — t-Bu O 2-Me-3-Br-5-CN-1H-pyrrol-1-yl Oil^(•)  51 Me R H — t-Bu O 2,3-diCl-5-CN-1H-pyrrol-1-yl 110-116  52 Me R H — t-Bu O 2,3,4-triCl-5-CN-1H-pyrrol-1-yl 110-116  53 Me R,S H — t-Bu CH₂ 3-Cl-5-CN-1H-pyrrol-1-yI  75-106  54# H — H — t-Bu CH₂ C₆H₅ 93-96  55# H — H — t-Bu CH₂ 2,3-diCl-5-CN-1H-pyrrol-1-yl Oil^(•)  56 Me R H — CH(Me)C(Me)₃ O C₆H₅ Oil^(•)  57 Me R H — CH(Me)C(Me)₃ O 2-F-C₆H₄ Oil^(•)  58 Me R H — CH(Me)C(Me)₃ O 2-Cl-C₆H₄ Oil^(•)  59 Me R H — CH(Me)C(Me)₃ O 2-Br-C₆H₄ Oil^(•)  60 Me R H — CH(Me)C(Me)₃ O 2-CN-C₆H₄ Oil^(•)  61 Me R H — CH(Me)C(Me)₃ O 2-(CH₂CN)-C₆H₄ Oil^(•)  62 Me R H — CH(Me)C(Me)₃ O 2,5-diCl-C₆H₃ Oil^(•)  63 Me R,S H — CH(Me)C(Me)₃ O 2-CN-3-F-C₆H₃ Oil^(•)  64 Me R,S H — CH(Me)C(Me)₃ O 2-CN-3-Cl-C₆H₃ Oil^(•)  65 Me R,S H — CH(Me)C(Me)₃ O 2-CN-3-I-C₆H₃ Oil^(•)  66 Me R,S H — CH(Me)C(Me)₃ O 2-CN-3-CF₃-C₆H₃ Oil^(•)  67 Me R,S H — CH(Me)C(Me)₃ O 2-F-6-CN-C₆H₃ 147-165  68 Me R,S H — CH(Me)C(Me)₃ O 2-CF₃-6-CN-C₆H₃ Oil^(•)  69 Me R,S H — CH(Me)C(Me)₃ O 2-CN-3,5-diF-C₆H₂ Oil^(•)  70 Me R,S H — CH(Me)C(Me)₃ O 2-Me-3-Br-5-CN-1H-pyrrol-1-yl Oil^(•)  71a Me R,S H — CH(Me)C(Me)₃ O 2-Me-3-Cl-5-CN-1H-pyrrol-1-yl Oil^(•)  71b Me R,S H — CH(Me)C(Me)₃ O 2-Me-3-Cl-5-CN-1H-pyrrol-1-yl Oil^(•)  72 Me R,S H — CH(Me)C(Me)₃ CH₂ 2-Me-3-Cl-5-CN-1H-pyrrol-1-yl 111-118 Ex. 4  73 Me R,S H — CH(Me)C(Me)₃ CH₂ 2-Me-3-Br-5-CN-1H-pyrrol-1-yl Oil^(•)  74 Me R,S H — CH(Me)C(Me)₃ CH₂ 3-Cl-5-CN-1H-pyrrol-1-yl Oil^(•) 165a# Me R H — t-Bu O 2-Br-4-F-C₆H₃ 95-98 165b## Me R H — t-Bu O 2-Br-4-F-C₆H₃ Oil^(•) 166a# Me R H — t-Bu O 2-Br-5-F-C₆H₃ 95-98 166b## Me R H — t-Bu O 2-Br-5-F-C₆H₃ 77-80 168a# Me R H — t-Bu O 2,3,5-triF-C₆H₂ 111-114 168b## Me R H — t-Bu O 2,3,5-triF-C₆H₂ 116-119 169a# Me R H — t-Bu O 2-Cl-3,5-diF-C₆H₂ 109-112 169b## Me R H — t-Bu O 2-Cl-3,5-diF-C₆H₂ Oil^(•) 170a# Me R H — t-Bu O 2,3,5-triCl-C₆H₂ Oil^(•) 170b## Me R H — t-Bu O 2,3,5-triCl-C₆H₂ 109-112 171a# Me R H — t-Bu O 2,3,6-triCl-C₆H₂ Oil^(•) 171b## Me R H — t-Bu O 2,3,6-triCl-C₆H₂ Oil^(•) 172 Me R H — t-Bu O 2,4,6-triCl-C₆H₂ 81-83 173a# Me R H — t-Bu O 4-Cl-2,5-diF-C₆H₂ 93-95 173b## Me R H — t-Bu O 4-Cl-2,5-diF-C₆H₂ 112-115 174a# Me R H — t-Bu O 2,4,5-triCl-C₆H₂ Oil^(•) 174b## Me R H — t-Bu O 2,4,5-triCl-C₆H₂ 139-142 175 Me R,S H — t-Bu O 2-(CH₂F)-C₆H₄ 139-142 176 Me R H — t-Bu O 3-Me-C₆H₄ Oil^(•) 177 Me R H — t-Bu O 3-Et-C₆H₄ Oil^(•) 181a# Me R H — t-Bu O 3,4-diCl-C₆H₃ Oil^(•) 181b## Me R H — t-Bu O 3,4-diCl-C₆H₃ Oil^(•) 182a# Me R H — t-Bu O 3-F-4-Cl-C₆H₃ Oil^(•) 182b## Me R H — t-Bu O 3-F-4-Cl-C₆H₃ Oil^(•) 183a# Me R H — t-Bu O 3-Cl-4-F-C₆H₃ Oil^(•) 183b## Me R H — t-Bu O 3-Cl-4-F-C₆H₃ 85-88 184a# Me R H — t-Bu O 3,5-diF-C₆H₃ 123-126 184b## Me R H — t-Bu O 3,5-diF-C₆H₃ 85-88 185 Me R H — t-Bu O 2-(CH₂CH═CH₂)-4-Me-C₆H₃ 84-86 186 Me R H — t-Bu O 2,3,6-triF-C₆H₂ Oil^(•) 187a# Me R H — t-Bu O 2-Br-3,4-diF-C₆H₂ 115-118 187b## Me R H — t-Bu O 2-Br-3,4-diF-C₆H₂ Oil^(•) 188a# Me R H — t-Bu O 2,4,5-triF-C₆H₂ Oil^(•) 189b## Me R H — t-Bu O 2,4,5-trif-C₆H₂ Oil^(•) 189a# Me R H — t-Bu O 2,4,6-triF-C₆H₂ 76-79 189b## Me R H — t-Bu O 2,4,6-triF-C₆H₂ Oil^(•) 190a# Me R H — t-Bu O 2,3,4-triF-C₆H₂ Oil^(•) 190b## Me R H — t-Bu O 2,3,4-triF-C₆H₂ Oil^(•) 191a# Me R H — t-Bu O 2-Cl-5-F-C₆H₃ Oil^(•) 191b## Me R H — t-Bu O 2-Cl-5-F-C₆H₃ Oil^(•) 191c Me R H — t-Bu O 2-Cl-5-F-C₆H₃ Oil^(•) 192a# Me R H — C(Me)₂CH═CH₂ O 2-Cl-5-F-C₆H₃ 79-81 192b## Me R H — C(Me)₂CH═CH₂ O 2-Cl-5-F-C₆H₃ Oil^(•) 193 Me R H — C(Me)₂C≡CH O 2-Cl-5-F-C₆H₃  99-102 194 Me R H — CH(Me)C(Me)₃ O 2-Cl-5-F-C₆H₃  99-102 195 Me R H — t-Bu O 2,3,5,6-tetraF-C₆H 81-83 196 Me R H — t-Bu O 2,6-diBr-4-F-C₆H₂ 130-133 197 Me R H — t-Bu O 2,6-diCl-4-F-C₆H₂ 120-123 198a# Me R H — t-Bu O 2-F-5-Cl-C₆H₃ 101-104 198b## Me R H — t-Bu O 2-F-5-Cl-C₆H₃ Oil^(•) 199 Me R H — CH(Me)C(Me)₃ O 2-F-5-Cl-C₆H₃ Oil^(•) 200a# Me R H — C(Me)₂CH═CH₂ O 2-F-5-Cl-C₆H₃ 104-107 200b## Me R H — C(Me)₂CH═CH₂ O 2-F-5-Cl-C₆H₃ Oil^(•) 201 Me R,S H — t-Bu O 2-(OCF₂CF₂H)-C₆H₄ Oil^(•) 202 Me R,S H — t-Bu O 2-(SCF₂CF₂H)-C₆H₄  80-110 203 Me R,S H — t-Bu O 2-F-6-CN-C₆H₃ Oil^(•) 204 Me R,S H — t-Bu O 2-(CH₂CH═CH₂)-6-CN-C₆H₃ Oil^(•) 205 Me R,S H — t-Bu O 2-(CH₂CH₂CH₃)-6-CN-C₆H₃ Oil^(•) 206 Me R,S H — t-Bu O 2-CF₂H-6-CN-C₆H₃ 93-145 207 Me R,S H — t-Bu O 2-CN-4,5-diF-C₆H₂  55-105 208 Me R,S H — t-Bu O 2-CN-3,6-diF-C₆H₂ 113-156 209 Me R,S H — t-Bu O 2-CN-6-Me-C₆H₃ Oil^(•) 210 Me R,S H — t-Bu O 2-CN-6-Cl-C₆H₃ 118-150 211 Me R H — C(Me)₂C≡CH O 2,5-diF-C₆H₃ 85-87 212 Me R H — C(Me)₂C≡CH O 2,5-diCl-C₆H₃ 93-97 213 Me R H — C(Me)₂C≡CH O 2-Cl-5-Me-C₆H₃ 84-86 214 Me R H — C(Me)₂CH═CH₂ O 2,5-diF-C₆H₃ 107-112 215a# Me R H — C(Me)₂CH═CH₂ O 2,5-diCl-C₆H₃  82-110 215b## Me R H — C(Me)₂CH═CH₂ O 2,5-diCl-C₆H₃ Oil^(•) 216 Me R,S H — t-Bu O 2-(C≡CH)-C₆H₄ 128-146 217 Me R H — C(Me)₂CF═CH₂ O 2,5-diF-C₆H₃ 106-110 Ex. 7 218 Me R H — C(Me)(CH₂F)CH═CH₂ O 2,5-diF-C₆H₃ 70-85 219 Me R H — C(Me)(CH₂F)CH═CH₂ O 2,5-diCl-C₆H₃ Oil^(•) 220 Me R H — C(Me)(CH₂F)CH═CH₂ O 2-Cl-5-F-C₆H₃ 73-88 221a# Me R H — C(Me)₂CH═CHF O 2,5-diF-C₆H₃ Oil^(•) 221b## Me R H — C(Me)₂CH═CHF O 2,5-diF-C₆H₃ Oil^(•) 222 Me R H — C(Me)₂CH═CHF O 2-Cl-5-F-C₆H₃ Oil^(•) 223 Me R H — C(Me)₂CF═CH₂ O 2-Cl-5-F-C₆H₃ Oil^(•) 224 Me R H — C(Me)₂CH═CHF O 2-F-5-Cl-C₆H₃ 78-86 225 Me R H — C(Me)(CH₂F)CH═CHF O 2-(OCF₂CF₂H)-5-F-C₆H₃ Oil^(•) 226 Me R H — C(Me)(CH₂F)CH═CHF O 2-F-5-Me-C₆H₃ 70-81 227 Me R H — C(Me)(CH₂F)CH═CHF O 2-Cl-5-Me-C₆H₃ Oil^(•) 320 Me R H — C(Me)₂C≡CH O 2-F-5-Cl-C₆H₃  98-101 275 Me R,S H — CH(Me)C(Me)₃ O 2-(CH₂CHCH₂)-6-CN-C₆H₃ Oil^(•) 276 Me R,S H — CH(Me)C(Me)₃ O 2-(CH₂CH₂CH₃)-6-CN-C₆H₃ Oil^(•) 277 Me R,S H — CH(Me)C(Me)₃ O 2-CN-5-(OCF₂H)-C₆H₃ Oil^(•) 278 Me R,S H — CH(Me)C(Me)₃ O 2-CN-4,5-diF-C₆H₂ Oil^(•) 279 Me R,S H — CH(Me)C(Me)₃ O 2-CN-3,6-diF-C₆H₂ Oil^(•) 280 Me R,S H — CH(Me)C(Me)₃ O 2-CN-6-Me-C₆H₃ Oil^(•) 281 Me R,S H — CH(Me)C(Me)₃ O 2-CN-6-Cl-C₆H₃ Oil^(•) 282 Me R H — CH(Me)₂CH═CH₂ O 2-F-5-Me-C₆H₃ 102-108 283 Me R C₆H₅ S CH₂CH═CH₂ O 2,5-diF-C₆H₃ Oil^(•) 284 Me R C₆H₅ S CH₂CH═CH₂ O 2-CN-5-F-C₆H₃ Oil^(•) 285 Me R C₆H₅ S CH₂CH═CH₂ O 2-CN-C₆H₄ Oil^(•) 286 Me R C₆H₅ S CH₂CH₃ O 2-CN-5-F-C₆H₃ Oil^(•) 287 Me R C₆H₅ S CH₂CH₂CH₃ O 2-CN-5-F-C₆H₃ Oil^(•) 288 Me R C₆H₅ S CH₂CH₂CH₃ O 2-CN-C₆H₄ Oil^(•) 289 Me R C₆H₅ S CH(CH₃)₂ O 2-CN-5-F-C₆H₃ Oil^(•) 290 Me R C₆H₅ S CH(CH₃)₂ O 2-CN-C₆H₄ Oil^(•) 291 Me R C₆H₅ S C(CH₃)₃ O 2-CN-C₆H₄ Oil^(•) 292 Me R H — C(CH₃)₃ O 2-(OCF₂H)-5-F-C₆H₃ Oil^(•) 293 Me R C₆H₅ R CH₂CH3 O 2,5-diF-C₆H₃ Oil^(•) 294 Me R H — CH(Me)₂CH═CH₂ O 2-(OCF₂H)-5-F-C₆H₃ Oil^(•) 295 Me R H — CH(Me)₂C≡CH O 2-(OCF₂H)-5-F-C₆H₃ Oil^(•) 296 Me R H — CH(Me)(Et)CH═CH₂ O 2,5-diF-C₆H₃  96-106 297 Me R H — CH(Me)(Et)CH═CH₂ O 2-F-5-Cl-C₆H₃ Oil^(•) 298 Me R H — CH(Me)(Et)CH═CH₂ O 2-Cl-5-F-C₆H₃  93-104 299 Me R H — CH(Me)₂CF═CH₂ O 2-F-5-Cl-C₆H₃ 115-123 300 Me R H — CH(Me)₂CF═CH₂ O 2,5-diCl-C₆H₃ 94-99 301 Me R H — CH(Me)(C≡CH)CH═CH₂ O 2,5-diF-C₆H₃ 84-92 302 Me R H — CH(Me)(C≡CH)CH═CH₂ O 2-F-5-Cl-C₆H₃ Oil^(•) 303 Me R H — CH(Me)(C≡CH)CH═CH₂ O 2-Cl-5-F-C₆H₃ 60-83 304 Me R C₆H₅ R CH₂CH₃ O 2-CN-C₆H₄ Oil^(•) 305 Me R H — t-Bu O 2-CN-5-t-Bu-C₆H₃ Oil^(•) 306 Me R H — t-Bu O 2-CH(Me)(Et)-C₆H₄ Oil^(•) ^(•)See Index Table E for ¹H NMR data. #Single diastereomer A. ##Single diastereomer B.

INDEX TABLE B

The compounds listed below are mixtures of diastereoisomers unless indicated otherwise. Con- Cmpd figuration No. R¹ at * R⁶ Z mp(° C.)  75 H — CH(Me)C(Me)₃ 2-F-C₆H₄ Oil^(•)  76 H — CH(Me)C(Me)₃ 3-Br-C₆H₄ Oil^(•) 167 H — t-Bu C₆H₅ 144-147 178 H — t-Bu 2-F-C₆H₄ 114-117 179 H — t-Bu 2-Cl-C₆H₄ 105-108 180 H — t-Bu 3-Cl-C₆H₄ 112-115 228 Me R,S t-Bu C₆H₅ Oil^(•) 229a# Me R t-Bu 2,5-diF-C₆H₃ Oil^(•) 229b## Me R t-Bu 2,5-diF-C₆H₃ Oil^(•) 272 H — t-Bu 3-Br-C₆H₄ 112-115 273 H — t-Bu 2,4-diF-C₆H₃ 122-125 274 H — t-Bu 2,4-diCl-C₆H₃ 83-86 307 Me R t-Bu 2-CN-C₆H₄ Oil^(•) 308 Me R t-Bu 2-F-C₆H₄ Oil^(•) 309 Me R t-Bu 2,4-diF-C₆H₃ Oil^(•) ^(•)See Index Table E for ¹H NMR data. #Single diastereomer A. ##Single diastereomer B.

INDEX TABLE C

The compounds listed below are mixtures of diastereoisomers unless indicated otherwise. Cmpd Config. No R¹ at* R² R³ R⁴ R⁵ X Z mp(° C.)  77a Me R,S H Et Me H O C₆H₅ 95-99  77b Me R H Et Me H O C₆H₅ 94-96  78a Me R,S H Et Me H O 2-F-C₆H₄ 94-96  78b Me R H Et Me H O 2-F-C₆H₄ 77-79  79a Me R,S H Et Me H O 3-F-C₆H₄ 110-113  79b Me R H Et Me H O 3-F-C₆H₄ 86-88  80a Me R,S H Et Me H O 4-F-C₆H₄ 104-107  80b Me R H Et Me H O 4-F-C₆H₄ Oil^(•)  81a Me R,S H Et Me H O 2-Cl-C₆H₄ 114-117  81b Me R H Et Me H O 2-Cl-C₆H₄ 96-98  82a Me R,S H Et Me H O 3-Cl-C₆H₄ 118-121  82b Me R H Et Me H C 3-Cl-C₆H₄ Oil^(•)  83a Me R,S H Et Me H O 4-Cl-C₆H₄ 121-124  83b Me R H Et Me H O 4-Cl-C₆H₄ 77-79  84a Me R,S H Et Me H O 2-Br-C₆H₄ 124-126  84b Me R H Et Me H O 2-Br-C₆H₄ Oil^(•)  85a Me R.S H Et Me H O 3-Br-C₆H₄ 83-86  85b Me R H Et Me H O 3-Br-C₆H₄ Oil^(•)  86a Me R,S H Et Me H O 4-Br-C₆H₄ 124-127  86b Me R H Et Me H O 4-Br-C₆H₄ 102-104  87a Me R,S H Et Me H O 2-I-C₆H₄ 108-111  87b Me R H Et Me H O 2-I-C₆H₄ Oil^(•)  88 Me R H Et Me H O 3-I-C₆H₄ 75-77  89a Me R,S H Et Me H O 2-CN-C₆H₄ 134-136  89b Me R H Et Me H O 2-CN-C₆H₄ Oil^(•)  90 Me R,S H Et Me H O 2-(OCF₂CF₂H)-C₆H₄ 90-98  91 Me R,S H Et Me H O 2-(SCF₂CF₂H)-C₆H₄ 61-76  92 Me R,S H Et Me H O 2-CH₂F-C₆H₄ 105-107  93 Me R,S H Et Me H O 3-CH₂F-C₆H₄ 123-125  94a Me R,S H Et Me H O 2-CF₃-C₆H₄ 131-132  94b Me R H Et Me H O 2-CF₃-C₆H₄ Oil^(•)  95 Me R H Et Me H O 2-Me-C₆H₄ Oil^(•)  96 Me R H Et Me H O 3-Me-C₆H₄ 80-82  97a Me R,S H Et Me H O 2-Et-C₆H₄ 102-105  97b Me R H Et Me H O 2-Et-C₆H₄ Oil^(•)  98a Me R,S H Et Me H O 2-n-Pr-C₆H₄ 90-92  98b Me R H Et Me H O 2-n-Pr-C₆H₄ Oil^(•)  99 Me R H Et Me H O 2-i-Pr-C₆H₄ Oil^(•) 100 Me R H Et Me H O 2-t-Bu-C₆H₄ Oil^(•) 101a Me R,S H Et Me H O 2-(CH₂CH═CH₂)-C₆H₄ 90-92 101b Me R H Et Me H O 2-(CH₂CH═CH₂)-C₆H₄ Oil^(•) 102 Me R,S H Et Me H O 3-CH₂F-C₆H₄ 105-107 103 Me R H Et Me H O 2-(CH₂CN)-C₆H₄ Oil^(•) 104 Me R H Et Me H O 2,3-diF-C₆H₃ 95-97 105a Me R,S H Et Me H O 2,6-diF-C₆H₃ 95-97 105b Me R H Et Me H O 2,6-diF-C₆H₃ Oil^(•) 106 Me R H Et Me H O 2.4-diF-C₆H₃ Oil^(•) 107 Me R H Et Me H O 2,5-diF-C₆H₃ 67-72 108 Me R H Et Me H O 3,4-diF-C₆H₃ Oil^(•) 109 Me R H Et Me H O 2,3,5-triF-C₆H₂ 86-88 110 Me R H Et Me H O 2,4,5-triF-C₆H₂ 69-71 111 Me R H Et Me H O 22-diCl-C₆H₃ 87-89 112 Me R H Et Me H O 2,4-diCl-C₆H₃ 70-72 113 Me R H Et Me H O 2,5-diCl-C₆H₃ 93-95 114 Me R H Et Me H O 2,6-diCl-C₆H₃ 87-89 115 Me R H Et Me H O 3,5-diCl-C₆H₃ 87-89 116 Me R H Et Me H O 2,3,5-triCl-C₆H₂ 94-96 117 Me R H Et Me H O 2,3,6-triCl-C₆H₂ 95-97 118 Me R H Et Me H O 2,4,6-triCl-C₆H₂ 118-121 119 Me R H Et Me H O 2-(CH₂CH═CH₂)-6-Me-C₆H₃ Oil^(•) 120 Me R H Et Me H O 2-F-4-Cl-C₆H₃ Oil^(•) 121 Me R H Et Me H O 2-Cl-4-F-C₆H₃ 65-67 122 Me R,S H Et Me H O 2-F-4-Br-C₆H₃ 107-109 123 Me R H Et Me H O 2-Cl-3,5-diF-C₆H₂ 84-86 124 Me R H Et Me H O 2-Br-4-F-C₆H₃ 62-64 125 Me R H Et Me H O 2-Br-5-F-C₆H₃ 73-75 126 Me R H Et Me H O 2-Cl-4-Me-C₆H₃ 73-74 127 Me R H Et Me H O 2-Cl-5-Me-C₆H₃ 102-104 128 Me R,S H Et Me H O 2-F-6-CN-C₆H₃ 102-106 129 Me R,S H Et Me H O 2-CN-4-F-C₆H₃ 119-123 Ex. 3 130 Me R,S H Et Me H O 2-CN-3-F-C₆H₃ 143-149 131 Me R,S H Et Me H O 2-CN-3-Cl-C₆H₃ 120-122 132 Me R,S H Et Me H O 2-CN-3-L-C₆H₃ 146-151 133 Me R,S H Et Me H O 2-CN-3-CF₃-C₆H₃ 120-138 134 Me R,S H Et Me H O 2-CN-6-CF₃-C₆H₃ 110-134 135 Me R,S H Et Me H O 2-CN-3,5-diF-C₆H₂ 164-166 136 Me R,S H Et Me H O 2-CN-3,5-diMe-1H-pyrrol-1-yl Oil^(•) 137 Me R,S H Et Me H O 3-Br-5-CN-1H-pyrrol-1-yl 130-146 138 Me R,S H Et Me H O 3-Cl-5-CN-1H-pyrrol-1-yl 108-112 139 Me R,S H Et Me H O 2,3-diCl-5-CN-1H-pyrrol-1-yl Oil^(•) 140a Me R,S H Et Me H O 2-Me-3-Cl-5-CN-1H-pyrrol-1-yl 107-117 140b Me R H Et Me H O 2-Me-3-Cl-5-CN-1H-pyrrol-1-yl Oil^(•) Ex.2 141 Me R,S H Et Me H O 2-Me-3-Br-5-CN-1H-pyrrol-1-yl Oil^(•) 142 Me R,S H Et Me H CH₂ 2-Me-3-Cl-5-CN-1H-pyrrol-1-yl 109-115 143 Me R,S H Et Me H CH₂ 2-Me-3-Br-5-CN-1H-pyrrol-1-yl 123-141 144 Me R,S H Et Me H CH₂ 3-Cl-5-CN-1H-pyrrol-1-yl Oil^(•) 145# H — H Et Me H CH₂ 1H-pyrrol-1-yl 71-78 146# H — H Et Me H CH₂ 2-Cl-1H-pyrrol-1-yl 98-100 147# H — H Et Me H CH₂ 2,5-diCl-1H-pyrrol-1-yl 105-110 148# H — H Et Me H CH₂ 2,3,5-triCl-1H-pyrrol-1-yl 131-133 149# H — H Et Me H CH₂ 2-CN-1H-pyrrol-1-yl Oil^(•) 150# H — H Et Me H CH₂ 2-CN-3,5-diMe-1H-pyrrol-1-yl 82-84 151# H — H Et Me H CH₂ 2,3-diCl-5-CN-lH-pyrrol-1-yl 138-142 152# H — H Et Me H CH₂ 2-Cl-5-CN-1H-pyrrol-1-yl Oil^(•) 153# H — H Et Me H O C₆H₅ 65-69 154# H — H Et Me H CH₂ C₆H₅ 93-95 155# H — H Et H Me CH₂ C₆H₅ 66-70 Ex. 1 230 Me R H Et Me H O 3,4-diCl-C₆H₃ Oil^(•) 231 Me R H Et Me H O 3-F-4-Cl-C₆H₃ Oil^(•) 232 Me R H Et Me H O 3-Cl-4-E-C₆H₃ 77-80 233 Me R H Et Me H O 2,3,6-triF-C₆H₂ 81-84 234 Me R H Et Me H O 3,5-diF-C₆H₃ 84-87 235 Me R H Et Me H O 2-Br-4,5-diF-C₆H₂ Oil^(•) 236 Me R H Et Me H O 2,4,5-triF-C₆H₂ Oil^(•) 237 Me R H Et Me H O 2,4,6-triF-C₆H₂ Oil^(•) 238 Me R H Et Me H O 2,3,4-triF-C₆H₂ Oil^(•) 239 Me R H Et Me H O 2-CN-5-Cl-C₆H₃ Oil^(•) 240 Me R H Et Me H O 3-Et-C₆H₄ Oil^(•) 241 Me R H Et Me H O 4-t-Bu-C₆H₄ Oil^(•) 242 Me R H Et Me H O 2,4,5-triCl-C₆H₂ 80-83 243 Me R H Et Me H O 2,3,4-triCl-C₆H₂ 82-85 244 Me R,S H Et Me H CH₂ C₆H₅ 105-108 245 Me R H Et Me H O 2-CN-5-F-C₆H₃ Oil^(•) 246 Me R H Et Me H O 2-CN-5-Br-C₆H₃ Oil^(•) 247 Me R H Et Me H O 2-CN-5-I-C₆H₃ Oil^(•) 248 Me R H Et Me H O 2-CN-5-t-Bu-C₆H₃ Oil^(•) 249 Me R H Et Me H O 2,3,5,6-tetraF-C₆H 92-95 250 Me R H Et Me H O 2,6-diBr-4-F-C₆H₂ 88-90 251 Me R H Et Me H O 2,6-diCl-4-F-C₆H₂ 85-88 252 Me R H Et Me H O 2-F-5-Cl-C₆H₃ 110-113 253 Me R H Et Me H O 2-Cl-5-F-C₆H₃  97-100 254 Me R,S H Et Me H O 2-(CH₂CH═CH₂)-6-CN-C₆H₃ Oil^(•) 255 Me R,S H Et Me H O 2-(CH₂CH₂CH₃)-6-CN-C₆H₃ Oil^(•) 256 Me R,S H Et Me H O 2-CN-5-(OCF₂H)-C₆H₃ Oil^(•) 257 Me R,S H Et Me H O 3,4-diF-6-CN-C₆H₂ Oil^(•) 258 Me R,S H Et Me H O 2,5-diF-6-CN-C₆H₂  98-108 259 Me R,S H Et Me H O 2-CN-6-Me-C₆H₃  97-114 260 Me R,S H Et Me H O 2-Cl-6-CN-C₆H₃ 90-92 310 Me R,S H Me Me H O C₆H₅ 70-75 311 Me R,S H Me H H O C₆H₅ Oil^(•) 312 Me R,S H Me H H O 2-CF₃-C₆H₄ Oil^(•) 313 Me R,S H Me H H O 2-Br-C₆H₄ Oil^(•) 314 Me R,S H Me H H O 2-(CH₂CH═CH₂)-C₆H₄ Oil^(•) 315 Me R,S H Me H H O 2-F-C₆H₄ Oil^(•) 316 Me R,S H Et Me H O 2-CN-6-F-C₆H₃ 87-94 317 Me R,S H Et Me H O 3-(CH₂F)-C₆H₄ 123-125 318 Me R H Et Me H O 2-Cl-3,5-diF-C₆H₂ 84-86 ^(•)See Index Table E for ¹H NMR data. #Single diastereomer.

INDEX TABLE D

The compounds listed below are mixtures of diastereoisomers unless indicated otherwise. Con- Cmpd figuration No R¹ at * X Z mp(° C.) 156# H — H CH C₆H₅ 109-111 157# H — H CH 2-F-C₆H₄ 103-105 Ex. 5 158# H — H CH 2-Cl-C₆H₄ 143-145 159# H — H CH 3-Cl-C₆H₄ Oil^(•) 160# H — H CH 3-Br-C₆H₄ Oil^(•) 161# H — H CH 2-(CH₂CN)-C₆H₄ Oil^(•) 162# H — H CH 2,4-diF-C₆H₃ Oil^(•) 163# H — H CH 2,5-diCl-C₆H₄ 170-172 164# H — H CH 2-thienyl 120-122 261 Me R,S H CH 4-F-C₆H₄ 90-92 262# H — H C(Et) 2,5-diCl-C₆H₃ Oil^(•) 263 Me R,S H CH C₆H₅ Oil^(•) 264# H — H CH 3-F-C₆H₄ Oil^(•) 265# H — Me CH C₆H₅ Oil^(•) 266 Me R H CH 2,4-diCl-C₆H₃ Oil^(•) 267a# Me R H CH 2,5-diF-C₆H₃ Oil^(•) Ex. 8 267b# Me R H CH 2,5-diF-C₆H₃ 102-105 Ex. 8 268# H — H C(Me) C₆H₅ Oil^(•) 269# H — H C(Et) C₆H₅ 120-123 270# H — Me CH 2,5-diCi-C₆H₃ Oil^(•) 271# H — H C(Me) 2,5-diCi-C₆H₃ Oil^(•) ^(•)See Index Table E for ¹H NMR data. #Singie diastereomer A ##Single diastereomer B.

BIOLOGICAL EXAMPLES OF THE INVENTION

Test compounds were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in the following tests. Spraying these 200 ppm test suspensions to the point of run-off on the test plants is the equivalent of a rate of 500 g/ha.

Test A

The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Elysiphe gramilis f sp. tritici, (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20° C. for 7 days, after which disease ratings were made.

Test B

The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20° C. for 24 h, and then moved to a growth chamber at 20° C. for 6 days, after which disease ratings were made.

Test C

The test suspension was sprayed to the point of run-off on rice seedlings. The following day the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27° C. for 24 h, and then moved to a growth chamber at 30° C. for 5 days, after which disease ratings were made.

Test D

The test suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20° C. for 24 h, and then moved to a growth chamber at 20° C. for 5 days, after which disease ratings were made.

Test E

The test suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20° C. for 48 h, and moved to a growth chamber at 20° C. for 5 days, after which disease ratings were made.

Results for Tests A-E are given in Table A. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls). A dash (−) indicates no test results. ND indicates disease control not determined due to phytotoxicity. TABLE A Cmpd. Test No A Test B Test C Test D Test E  1a 60 0 53 0 0  1b 34 11 74 0 0  1c 60 85 73 16 0  1d 92 0 100 0 0  1e 92 0 100 80 47  2a 0 0 86 0 55  2b 0 0 100 0 0  2c 86 0 100 24 0  3a 85 0 94 0 55  3b 0 0 86 32 0  3c 38 0 100 4 0  3d 92 0 100 99 0  3e 86 0 100 68 0  4a 0 67 99 66 0  4b 86 0 99 89 82  4c 35 0 94 0 58  5a 0 68 0 0 0  5b 0 86 100 24 0  6a 0 0 74 0 0  6b 38 68 53 4 0  6c 0 0 97 9 0  6d 77 28 97 0 0  6e 0 0 100 96 70  7a 77 85 91 89 0  7b 77 0 74 89 47  7c 0 0 86 9 45  7d 62 68 99 0 6  8a 0 0 85 0 7  8b 37 0 100 89 47  8c 0 0 100 0 0  9a 0 0 53 0 0  9b 62 68 99 28 0  9c 62 28 100 51 0  10a 0 27 86 23 0  10b 62 67 86 95 0  10c 0 86 53 35 0  10d 77 0 74 35 45  11a 77 0 97 0 82  11b 77 85 99 23 0  12a 86 68 91 0 0  12b 77 0 94 68 0  13a 34 0 51 0 0  13b 0 0 86 4 83  14a 0 0 94 45 58  14b 61 0 86 23 0  15a 0 28 97 92 86  15b 0 0 97 45 0  16 0 0 97 48 0  17a 85 67 30 16 0  17b 38 28 100 0 0  18a 0 0 91 0 0  18b 77 0 94 0 0  19 0 0 97 0 0  20a 63 0 97 70 0  20b 0 0 100 0 0  21a 38 68 99 4 0  21b 37 27 99 — 0  22 0 0 100 0 0  23 0 0 97 48 0  24 62 0 53 66 94  25a 95 28 32 0 0  25b 63 0 97 24 0  26a 38 28 97 51 0  26b 38 68 100 81 0  27a 38 0 100 81 0  27b 91 0 100 0 0  28a 38 28 100 68 0  28b 86 28 100 96 0  29a 0 0 74 35 6  29b 0 0 100 23 0  30a 0 0 100 0 0  30b 77 27 97 0 0  31a 62 68 74 51 0  31b 0 0 94 0 0  32a 0 27 91 0 0  32b 0 27 94 23 0  33a 0 0 97 0 0  33b 0 67 100 80 0  34 62 85 91 0 0  35a 0 0 74 80 0  35b 37 0 91 0 0  36a 0 27 99 89 0  36b 62 27 100 80 0  37a 62 68 100 68 0  37b 77 68 99 96 0  38 0 28 53 0 22  39 0 0 86 2 0  40 21 0 86 0 0  41 62 0 97 66 47  42 0 0 53 2 0  43 0 0 86 66 0  44 0 0 94 89 0  45 0 0 86 0 0  46 0 0 53 66 0  47 0 0 53 52 0  48 0 0 91 0 0  49 0 0 0 0 0  50 86 28 53 57 0  51 71 0 53 68 0  52 71 86 0 81 0  53 0 0 53 0 0  54 34 11 32 0 16  55 0 0 85 0 0  56* 74 0 85 0 0  57* 91 0 85 0 0  58* 57 0 52 0 0  59* 0 0 52 0 0  60* 91 0 0 0 0  61* 74 0 73 0 0  62* 74 0 52 0 0  63 0 0 0 2 0  64 0 0 53 2 0  65 0 0 0 2 0  66 0 0 0 69 0  67 0 0 0 92 0  68 62 27 86 82 0  69 0 0 53 2 0  70 63 0 0 13 0  71a 0 0 53 19 0  71b** 0 0 0 19 0  72 0 0 91 0 0  73 30 28 53 0 11  74 0 86 53 23 0  75* 0 0 52 19 0  76* 0 0 0 19 0  77a 73 28 86 — 0  77b* 33 0 74 0 0  78a 0 93 90 0 74  78b 84 0 99 — 0  79a* 0 0 53 0 0  79b* 0 0 100 0 0  80a* 0 0 86 20 0  80b* 83 0 97 0 0  81a 0 0 0 0 55  81b* 85 0 74 0 0  82a* 0 0 53 43 0  82b 31 0 97 15 0  83a* 0 0 32 0 0  83b* 52 0 53 0 0  84a* 29 0 0 20 0  84b* 57 28 73 75 0  85a 55 0 53 — 0  85b* 0 0 53 0 0  86a* 0 67 0 0 0  86b* 52 0 0 28 0  87a* 0 0 74 0 0  87b* 52 0 0 0 0  88* 52 0 0 0 0  89a 0 0 74 20 0  89b 26 68 91 — 47  90 84 0 32 0 0  91 74 0 53 0 0  92* 60 0 0 0 0  93* 57 0 85 19 0  94a 0 0 0 0 0  94b* 71 0 0 0 0  95* 52 86 94 0 0  96* 0 0 0 90 0  97a* 0 0 0 20 0  97b* 71 0 53 0 0  98a 0 0 53 24 0  98b* 52 0 74 0 0  99* 83 0 0 68 0 100* 52 0 0 0 0 101a 0 0 0 46 22 101b* 0 0 0 0 0 102* 60 0 0 0 0 103 0 26 53 0 0 104* 84 0 97 0 0 105a 0 0 53 0 55 105b* 21 0 74 0 0 106* 84 0 97 19 0 107* 71 0 100 0 0 108* 57 0 94 0 0 109* 52 0 53 0 0 110* 90 0 97 0 0 111* 90 0 0 90 0 112* 71 0 0 0 0 113* 0 0 97 19 0 114* 83 0 0 0 0 115* 52 0 32 0 0 116* 21 0 0 0 0 117* 83 0 74 0 0 118* 83 0 0 0 0 119 31 0 32 0 0 120* 29 0 52 19 0 121* 71 0 53 0 0 122 0 0 0 0 0 123* 90 0 53 0 0 124* 83 0 0 0 0 125* 90 0 99 0 0 126* 0 0 73 0 0 127* 0 0 94 19 0 128 86 0 74 13 0 129 38 26 74 0 0 130 0 0 32 2 0 131 0 0 53 52 0 132 0 0 0 2 0 133 0 0 0 0 0 134 0 0 0 30 0 135 0 0 53 2 0 136 34 0 78 0 0 137 0 0 53 0 0 138 0 0 53 13 0 139 71 0 91 0 0 140a 29 0 90 0 0 140b 63 28 74 38 0 141 38 68 74 84 0 143 0 0 53 0 0 144 0 28 53 0 0 145 0 9 0 20 0 146 0 22 0 0 0 148 0 0 74 0 0 149 30 27 53 0 0 150 0 0 60 0 87 151 0 0 91 — 0 152 55 68 86 — 0 153 92 64 94 92 0 154 52 0 52 0 0 155 71 0 86 23 0 156* 0 0 0 0 0 157* 0 0 97 0 0 158* 0 0 52 0 0 159 0 0 0 0 47 160* 57 86 52 85 0 161* 0 0 0 0 0 162 0 0 74 95 82 163* 0 0 52 42 0 164 0 0 72 56 7 165a 86 0 74 23 86 165b 95 0 94 23 95 166a 0 0 99 76 58 166b 0 0 99 0 0 167 0 0 74 23 0 168a 76 0 74 0 58 168b 95 0 94 45 86 169a 84 27 91 24 0 169b 0 0 97 0 0 170a 35 0 53 0 58 170b 61 68 53 23 95 171a 0 0 86 0 0 171b 91 0 53 0 58 172 0 0 86 0 95 173a 63 28 52 33 0 173b 0 0 90 91 0 174a 0 0 31 54 0 174b 0 28 52 91 0 175* 0 0 74 33 0 176 77 0 94 56 6 177 62 0 94 35 6 178 0 0 53 0 58 179 35 0 74 23 58 180 61 0 74 76 0 181a 0 0 86 56 69 181b 37 0 74 0 90 182a 0 0 0 0 0 182b 0 68 94 0 0 183a 0 28 86 35 0 183b 86 28 94 35 69 184a 62 0 74 0 6 184b 62 0 74 9 45 185 0 28 86 9 45 186 0 0 100 0 45 187a 0 28 94 9 6 187b 77 68 94 91 6 188a 0 0 97 56 0 188b 0 0 100 35 45 189a 0 0 97 0 6 189b 0 0 100 35 0 190a 0 0 91 0 6 190b 0 0 94 0 0 191a 0 0 100 25 85 191b 0 0 100 47 55 191c 86 0 100 23 0 192a 0 0 100 0 85 192b 0 0 100 0 0 193 0 0 100 0 55 194 0 0 100 0 0 195 85 0 99 32 — 196 0 0 86 0 — 197 59 0 86 0 — 198a 75 28 100 5 — 198b 59 28 100 5 — 199 85 68 97 5 — 200a 0 0 100 5 — 200b 0 0 100 5 — 201 90 0 53 46 0 202 0 0 53 0 0 203 0 28 91 0 0 204 0 0 74 0 0 205 0 68 74 0 0 206 0 0 74 0 0 207 0 0 0 0 0 208 0 28 94 45 0 209 0 0 86 0 0 210 0 0 91 0 0 211 63 0 100 76 0 212 0 0 100 23 0 213 63 0 99 62 0 214 0 0 100 23 0 215a 63 0 99 45 0 215b 0 28 99 76 83 216 0 0 99 9 45 217 0 0 99 0 0 218 86 68 100 17 0 219 86 86 99 96 0 220 0 0 100 85 0 221a 0 0 100 41 0 221b 62 68 100 41 0 222 62 28 100 41 0 223 62 28 100 41 0 224 85 0 100 5 — 225 91 86 100 5 — 226 0 0 100 0 — 227 0 0 100 0 — 228 95 0 52 7 47 229a 0 0 100 0 55 229b 0 0 100 25 95 230 0 0 53 0 45 231 0 0 97 0 93 232 62 0 100 35 69 233 62 0 94 9 6 234 0 0 100 0 0 235 0 0 91 0 ND 236 77 0 97 0 0 237 62 0 53 9 0 238 62 0 74 0 ND 239 0 0 97 88 0 240 63 0 94 96 0 241 38 0 74 74 0 242 0 0 74 96 0 243 38 0 74 74 0 244 86 0 99 74 0 245 72 0 100 0 0 246 53 0 97 0 0 247 53 0 85 0 0 248 53 0 90 62 83 249 0 0 94 0 0 250 0 0 52 0 85 251 0 0 94 0 0 252 0 0 99 5 — 253 59 0 100 0 — 254 0 0 53 0 0 255 28 0 74 0 0 256 56 0 0 0 0 257 0 0 0 0 0 258 74 27 94 0 0 259 84 0 91 0 48 260 0 0 74 24 83 261 0 0 100 54 0 262 98 0 53 99 0 263 86 0 86 33 0 264 0 0 90 54 94 265 77 0 91 96 0 266 63 0 91 74 0 267a 78 0 97 0 55 267b 92 0 100 0 55 268 38 0 91 88 0 269 98 0 94 74 0 270 77 0 91 96 0 271 77 0 94 96 0 272 76 0 53 63 0 273 86 0 53 23 0 274 61 28 74 23 58 275 0 0 53 0 99 276 0 0 0 0 94 277 0 0 0 0 0 278 56 67 32 0 94 279 56 0 0 0 0 280 56 0 74 0 0 281 56 0 53 0 0 282 0 0 100 24 0 283 0 0 99 0 0 284 0 0 99 0 0 285 59 0 97 0 0 286 76 0 99 0 0 287 0 0 97 23 0 288 33 0 86 0 0 289 0 0 90 45 0 290 59 0 90 0 0 291 0 0 90 0 0 292 0 0 99 46 0 293 0 0 100 23 0 294 0 0 99 24 0 295 0 0 100 0 0 296 0 0 100 24 0 297 0 0 100 46 0 298 62 0 99 99 0 301 62 0 100 24 0 302 0 0 99 24 0 303 0 0 99 100 0 304 0 0 97 0 0 305 0 0 53 0 0 306 0 67 99 0 94 307 36 0 94 0 0 308 86 28 100 45 0 309 86 0 91 23 0 310 84 25 53 0 18 311 84 0 0 0 0 312 0 0 0 82 0 313 0 0 26 32 47 314 0 0 72 0 0 315 60 99 51 16 0 316 0 0 53 0 0 317* 57 0 85 19 0 318* 90 0 53 0 0 320 59 68 100 0 — *Tested at 40 ppm. **Tested at 100 ppm. 

1. A compound selected from the formula 1,

wherein Q is

Z is

X is —CH(R¹¹); R¹ is H; R² is H; R⁶ is C₂-C₆ alkyl, C₂-C₆ alkenyl, C_(2-C) ₆ alkynyl or C₃-C₆ cycloalkyl each optionally substituted with halogen or CN; R⁷ is H or halogen; R⁸ is H, R⁹ is H or halogen; and R¹¹ is H.
 2. (canceled)
 3. (canceled)
 4. (canceled)
 5. (canceled)
 6. (canceled)
 7. (canceled)
 8. (canceled)
 9. A fungicidal composition comprising a fungicidally effective amount of a compound of claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.
 10. A method for controlling plant diseases caused by fungal plant pathogens comprising adding to the plant or a portion thereof, or to the plant seed or seedling, a fungicidally effective amount of a compound of claim
 1. 11. A composition comprising a compound having the formula,

wherein Q is

Z is

R¹ is H; R² is H; R⁶ is C₂-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl or C₃-C₆ cycloalkyl each optionally substituted with halogen or CN; R⁷ is H or halogen; R⁸ is H, R⁹ is H or halogen; and R¹¹ is H; and at least one of a surfactant, a solid diluent or a liquid diluent.
 12. The composition of claim 11 wherein the composition is in a form selected from the group consisting of liquid, powder, emollient, aerosol, and granules.
 13. A method of treating a plant wherein the method comprises contacting at least a portion of a plant with an effective amount of the composition of claim
 12. 